SYNTHETIC RUBBERS

SYNTHETIC RUBBERS
GP
SBR,BUTYL RUBBER
SYNT POLY ISOPRENE
POLY BUTADIENE
WEATHER RESISTANCE
EPR, MODIFIED PE,
CHLORO SULPHONATED PE

 OIL RESISTANCE
POLY CHLORO PRENE RUBBER
NITRILE RUBBER
POLY SULFIDE RUBBER
ACRYLIC RUBBER
PU RUBBER
HEAT RESISTANCE
SILICONE RUBBER
FLOURO CARBON RUBBER

SBR
MORE THAN HALF OF THE WORLD PRODUCTION &
EXCEEDS THAN THAT OF NATURAL RUBBER
GRS- GOVT RUBBER STYRENE
DURING II WORLD WAR DEVELOPED
STYRENE : ETHYLENE + BENZENE TO
ETHYL BENZENE, DEHRATED (-H2O) WITH IRON
OXIDE GIVES STYRENE
BUTADIENE : FROM PETROLEUM BY THERMAL
CRACKING

 ALSO
AIR CAT
ETHANOL
CH3CHO +H2O
CAT
CH3CHO + C2H5OH
CH2=CH-CH=CH2 + H2O

POLYMERIZATION
STY (25%) + BUTA DIENE (75%) SBR
AT COLD 5-10 c COLD SBR BETTER
ABRASION REISITANCE
AT 5O C HOT SBR RUBBER
RANDOM COPOLYMER
CAT: P-METANE HYDRO PEROXIDE +
FERROUS SULFATE +
POTASSIUM PERSULFATE

STRUCTURE
SBR IS A RANDOM COPOLYMER
BUTADIENE UNIT ARE PRESENT ABOUT
20% -1,2 CONFIGURATION,
20% 1,4-CIS & 60% 1,4-TRANS
Because of irregular structure it does not
crystallize

Compounding and characteristics

Similar to Natural Rubber
Fillers, vulcanizing systems, antioxidants
and antizonants are used
Emulsion SBR is general purpose rubber
and can be blended with any other rubber
And possess cure compatibility
It has certain weaknesses as compared to
natural rubber such as less strength and
resilience and its heat build-up is greater

 A reinforcing filler is essential to get good

physical properties
It has good points as better abrasion resistance
Its quality tends to be more uniform and cleaner
Road holding properties are superior
Weatherability better
Chiefer than Natural rubber
The pactice orevalent is to use blends of SBR
with Natural Rubber

Applications
Three fourth of SBR produced finds
application in tyre manufacture.
Remaining in footwear, mechanical
goods, hoses/conveyor belts, adhesives,
etc

Solution SBR
Cat : Alkyl Lithium Solvent : Hydrocarbon
Narrow Mol.Wt Distribution, higher Mol.wt
And higher cis 1,4 butadiene than
emulsion SBR
More Loading of Carbon Black and Oil
Desirable properties such as crack
resistance and tread wear also improved

Formulation for tyre treads

SBR 1717
BR 1252
ISAF HS Black
Stearic Acid
Zinc Oxide
Sulfur
Antozite 67
Press cure at 160 C

Radial
82.5
55
70
2
3
1.75
1
13 min

Physical properties

Stress at 300% MPa 5.4

Tens St Mpa
16.6
Eb
%
580
Shore Hardness
60
Rebound % at 23 c
48.3

Poly butadiene

Formerly made from alcohol Ethanol

However now derived from petroleum
Cis-1,4 is more important as rubber
All other isomeric forms have poor physical
properties

Manufature in 1930 from Sodium metal is not

useful as rubber Low temp resistance is not
good Tg -45 deg C

 Similar to Emulsion SBR , emulsion PB was

tried
But these rubber had poor processability
But may be cheaper than solution BR
The problem was solved by the advent of
Zieglar Natta catalyst polymerization
Better streo-regularity. Coordination &
anionic solution Polymzn Techniques.
Solvent : n- heptane

Properties

Excellent dynamic properties

Low hysterisis
Good Abrasion Resistance
Tg = -102 deg C
Excellent Low Temp Performance
High Resilience
Blends with Natural Rubber & SBR upto 40-50%
Otherwise poor skid resistance
SBR +PB Increased abrasion & Tear resistance

Can be used as truck treads

Low m.p. green strength is low
Can not easily mixed on a roll mill
The band formed around the mill roll will
easily tear
Hence it is used with NR and SBR blends
only
Alone not much used

Butyl rubber

Butyl rubber

Butyl Rubber

Introduced in 1942
Isobutylene + iso prene 1-3% copolymerization
Alcl3 cat in methy chloride at - 95 Deg C
< seconds(1-2) Polymerizes
Liquid Ethylene is boiled thro reactor cooling
Coils to maintain temp
Mol wt 2-3,00,000 controlled by Chain transfer
agents
Trans 1,4 linear isoprene
Crystallizes on stretching

 Less Unsaturation
Unique age resistance , To oxygen, Ozone,
moisture & chemicals
Impermeable to Air
Applications
Inner tubes
Mechanical goods
High quality Electrical Insulation due Ozone,
moisture resistance

 Acid resistance & low resilience

So vibration dampers
Heat Resist, weather resistance, ozone Resist
are outstanding. But EPDM offers same prop
and prefered. Inj moldable.
Halogenated, CIIR, BIIR are more compatible
with NR & SBR
Prefered inner tube liners in tubeless tires
Curable by radiation( non-toxic)-medical goods

Other Appln :
Conveyor belts for carrying hot materials
adhesives , side walls of tyres
acid resistant tank liners
steam hoses

Modfied rubbers
Liquid rubbers(NR, BR, PIB, CR, NBR, PSulf,
silicones, PU, EPDM)
Low Mol wt of few thousands 2000-40000,
Viscosity 50,000 few lakhs Centi poise ( But
latex very high mol wt)
Prepared in the form of a liquid
Two types: first Generaton without Funtional
groups
And Second Generation with functional groups
OH, -SH, COOH reactive end types

First generation
Can be mixed in light machinery
Cast into the required shape and cured
with high cross-linking agents to achive
satisfactory level of prop.
Dioximes + Pbo2 at Room temp curing
However, 3D Net work is less perfect &
have less Ten st, Eb, Flex cracking
Resitance

Applications
Coatings, caulks, sealants, Models, Toys
Manufacture :
1) polymerization to give low molwt
2) By Termal Degra dation at 240 Deg c /
for few hrs
By Photo chemical Degradation
(+Hydrogen peroxide to OH termnated
Liquid NR for 2nd Generation)

2 generation
nd

-OH,

-COOH, -SH or amine groups

Cured and chain extended like ureathanes
Better Network and properties than liquid rubber 1st
generation
useful as curing agents- for epoxy resins
HTPB, CTPB, CTBN, HTNR
Polymer can cured with di iso cynates and aromatics
Rocket propellant binders , sealants,
Lighter vehicle tyres,

properties

Poor elastics and High Cost

Compresion set poor
ADV:
Can be processable in liquid proc
equipment RIM (Reactin Inj Moulding)for
PU
Light m/cs Automatic , less labour
reqirement
Economic : few thousands per day

Powderd Rubber
Cryo grinding / below Tg cooling and grinding
Become powder but recombines back
So inert fillers caco3, mica are used 10-15%
helps staibilizing the powders
Eliminates bale cutting operation
Easy blending and incorp of fillers
Less heat generation
more loading of accelerators and faster curion
Less scorch Danger

 Usable continuous mixing ( difficult in bulk

Form) by Extruders
Mixing and extrusion in the same M/c
Cost high , Due to Liquid Nitrogen
Spray drying of Emulsion /latex

Weather Resistance Rubbers

EPM - Ethylene Propylene rubber
EPDM - Ethylene Propylene Diene Monomer
Rubber
EPM
Ethylene + Propylene Special Zieglar Natta
Catalysts Vocl3+ Et2Alcl3
Oridinary Z-N cat not effective since E
polymerizes very fastly Than That of P
Solvent: Hexane, heptane, octane

 Copolymer composition is dependent on

Polymerization time, cat conc, Al: V ratio
Molwt Increases with Reaction time , E &
P ratio
Decreases with Temp, Cat conc
Comonomers: 1,4 Hexa diene, (HD)
Di cyclo penta diene, (DCPD),
Ethylidiene Nor borane (ENB)

 These monomers not Gels

Buta dienes Gels
ENB 10 times more expensive than DCPD, most
popular, & cures faster, easy to incorporation
favourable to co-curing with SBR for blending
DCPD Least expensive but has methine groups
and cause more chain scissons-may affect cure
efficiency
1,4 HD provides best ozone resistance & heat
resistance & easy for recycling
For fast curing 8-10%, generally 4-5% required

 Ethylene content 45 to 75%

If more E conc leads to better extrusion,
lower die swell, better shape retention but
impairs ease of mixing
More PP easy mixing, milling & molding
E contents contributes to higher viscosities
& better mechanical properties, shows
some crystalline regions, hence better
mech prop., have branches

 EPM less branched

EPDM- more branched due to dienes- double
present in the side chain
But not susceptible to chain scission unlike
Natural R, SBR, IIR
Heat resistance very higher than IIR
EPDM lowest density low weight
Tg close to SBR
Resilience Better than SBR, Much better than
IIR

 EPDM-oil & fillers-CB, Talc, silicates larger

amounts
Oils _Napthenic oils will not impair age
resistance
The Cost can be reduced with fillers
High perfom like Heat resist, weather Resist,
ozone resistance
Low Unsaturation & lack of polar groupsleads to excell electrical prop.
Mixing First CB & oil then Rubber

 Shearing will be easy in banbury mixer and some

stiffness will be present
Tackifier Required
Properties
Outstanding resistance to
heat, ozone, wheather
Excell electrical properties
Good resist to ply substract upto 100 C
& steam (160 C) in the absence of Oxygen
Good mech Prop & abrasion & flex cracking

 Peroxide curing better heat resist

S can cure
Anti Oxidant better effect on peroxide cured
component than Sulfur cured systems
EPDM- can work as antizonant for SBR & NR
Needs no co curing Immisible phase and
dispersed as small particles and stops ozone
attack

Applications
Tyre side walls
Inj molding, many automotive
components, low viscous at high Temp
for inj molding easy uncurable
Extrusion products- window seals, radiant
hoses, welding hoses,
Blends with EPDM Automobile Tubes
tyre curing bladders

 Tank liners-acid, alkali, Synth hydralic

fluid, animal fats & polar solvents
upto 100 C & 160 c for steam
Side wall tyre light colour retention
High flex reisist & weather resistance .
Agricultural comp replace NR, SBR, IIR

EVA
Ethylene Vinyl acetate
Ethylene + vinyl acetate / Methyl Acrylate
Polar and useful as elastomers
Manufacture :
Free radical or anionic polymzn
Properties:
Depends upon VA content 40-60 shows
elatomers
< 25% like Thermo plastics
Elastomeric behaviour due to -OCOCH3 side chain
which prevents crystallization

Properties
Brittle point -50 C , higher than EPDM
Specific gravity 0.98 Mooney viscosity <55
Polymer Saturated , hence heat
resistance, ozone and oxygen Resistance,
Weather resistance very Good Better
than NBR.
But solvent resistance lower than NBR &
CR( inspite of polarity)

 Hence Combination of Heat & solvent

Resistance
At 120 C Unlimited, at 150 C about A
Year, several weaks at 180-200 C
HR surfaces only by silicones & fluoro
carbon rubbers and in the absence of O2
better than Silicone rubber
Resists hot water & super heated steam
but affected by conc acids & alkalis

compounding
Eva available in granular form
Thermoplastics like mixing & compounding
Equipments at higher production rate
Some grades don t require curing, though
peroxide cure do better set & heat
resistance ( di tert butyl P O)
Mech Prop: Good with reinforcement fillers
Eb high, but resilience is not high unless
cross link density is sufficiently high

 Abrasion resist is not so good &

Tear resis is not so high
Will Pose problem while de molding
Non toxic FDA Approved Food contact
application possible
Curing by per oxide + tri allyl cyanuarate
co agent Inc cure rate Temp 170-200 C

Prop
Electrical prop- Semi conducting range
E +9-13 ohms- moderate values of resistivity
Good ESCR, flexibility-Replace PE in some
plastics products
Applications
Cable Insulations for medium voltage
While burning does not release toxic gases,
smoke un like PVC (HCL, Cl)

 So Insulating wires for under ground rail way

stations & High rise buildings
Hawai chappals- inj moulding
Bright colours attractive surface finish, so better
than NR
Hoses, Tubes- flexibility & stress cracking resist
than PE, PP
Packing rubber compounding additives . Direct
feeding to ban bury mixer & compatible than PE
packs

 PVC-EVA Permanent Plasticizer , Impact

modifier Food contact appln
Hot melt adhesives emerging field
No solvent hazardous
Good strength on cooling & much better
than SBS block copolymers
Low cost than SBS
Roofing sheets, medical goods, asphalt
modifications

Poly acrylate (ACM)

Polar ester groups- exhibits good solvent
and heat reisitance
First Good rich in 1940s
Ethyl acrylate , Butyl acrylate as monomers
Tg of PEA -22 C PBA -56 C
Alkyl side chain increases Tg lowers but
solvent resistance decreases

 EA +BA + Methoxy Ethyl or Ethoxy ethyl

acrylate Tg will decrease
Cure site Acrylic acid, Acrylo nitrile,
Chloro Vinyl Acetate, Chloro ethyl Vinyl
ether, Glycidyl allyl ether

manufacture
Free radical emulsion Polymerization
Copolymer Random Does not crystallize
on stretching
S.G. 1.1
Thermoplastics mixing behaviour- internal
mixing
Calender & extrude smoothly
Needs reinforcing fillers optimum mech
properties

Curing
Depends upon third monomers
Cl methyl Vinyl ether Amines , Poly amines(Tri
EthyleneTetra Amine), Thio urea, + Sulfur+ metal
oxides improves Heat resist and scorth
resistance
TETA +S+MBTS,
S 0.3 phr + K stearate 3 phr conveneint and
flexible
If any one conc varies improves ageing
resistance

 Post curing -optimum properties

Properties
Heat resistance 200 C to -28 C
Resist oxidation at even high temp
Good ozone, weather & flex resistance
Solvent , oil resistance
Oil + Fuel +S No brittle; NBR brittle, slowly
reacts. ACM No such Dis adv

 Low Gas permeability

Retain light colours
No toxic fumes on burning
Applications
Auto motive Under the hood
Mainly hoses, seals, Transmission seals, crank
shafts beltings, coatings ,adh, Vibration damping
mounts

Ethylene Methyl Acrylate

An acrylate rubber
Ethylene + Methyl acrylate + Acrylic Acid
Solution polymerization
AA cure site

Tg -46 C(50:50 %) ,depends upon Methyl

Acrylate content
If MA inc more polar and oil resist inc
When more ethylene better mechanical prop

 Proc : like Thermoplastics

Curing : by peroxides and amines
Often methylene di aniline or Hexa
methylene diamine
Accelerator : guanidine Zno should br
avoided due high reactivity of COOH
groups

Prop
Oil resist poorer than NBR but
comparable to CR
Upper serv temp 200 C
ACM CP BA-MA, not recommended
in contact with steam or acid or
alkali
Hence to some extent EMA is useful

Oil resistance Rubbers

Poly sulfide rubber
First discovered Solvent Resistance
rubber in 1930S
ExcellentSolvent & oil Resistance
Surpassed by any rubber
Major dis adv poor mech prop, poor heat
resistance & bad odour during processing
Polymerization : By condensation of alkyl
di halides & sodium poly sulfides


n cl R - cl + n Na2Sx -
-(-R Sx-)n + 2 n Nacl

 Reaction- by slow addition of di chloride to a

solution of sodium poly sulfide at 70 C
Mg(OH)2 protective colloid-polymer forms in
latex stage- from which rubber is coagulated.
Ethylene di chloride , di chloro propane, Bis(2chloro ethyl) ether or glycerol, or 1,3 dichloro
hydrin
x may be 2-4 in Sx
Grades FA & A High molwt & masticated in
chemicals for easy processing.

 In latex stage Na sulfite or HS hydro

sulfide can cleave the bonds and reduce
mol wt & liquid rubber of low mt forms.
Tri chloro propane leads branched
structure (Thiokol ST)
Thiokol A & FA -OH Terminated formed by
hydrolysis of terminal chlorine in the
alkaline medium of sodium poly sulfide

 When high mol wt decomposes to liquid

rubber with SH group in the latex Thiokol
ST grade.
Thiokol A & FA -plasticized by MBTS
which cleaves S-S- links & can be cured
by ZnO.
Cured polymer is high molwt & have high
compression set. After cooling only
moulding should be removed.

 Polymers SH groups can be cured by

oxidative linkage

O2
2 R-S-S-H -- R-S-S-R + H2O
With metal oxides ZnO, quinone dioxime
network cross linked & taken out of mold
even when hot

Prop
50-60 phr SRF black FEF give stength
Processability 10-20 phr CR-NBR or NR
or liquid PS rubber
Fully saturated, Hence have Excellent
ozone, weather resistance
More Sulfur, more polar, have more
solvent resistance
Less permeable to air & gases

 But less resistance to low temp & less resiliency

. However some grades have good LT prop
Formerly used as windows sealing in air-crafts
but today replaced by silicones
Thiokol FA & ST- resist even aromatic oils, dil
acids, but not dilute oxidizing acids
Thiokol DA bis (2-chloro ethyl ) ether 47%S
S.G 1.34
A- 85% S- s.g 1.6%, : A- 37%, sg 1.27( 2-chloro
ethyl formal +1,2,3 Tri chloro prpane)

applications

Due to solvent resistance

Printers roller, Sealants, hoses
Diaphragms for gas meters
Corrosion resit coatings
Liquid thiokol rubber- castings, adhesives
Binders to rocket fuels ,
Flexible mouldings, impact modifiers for
epoxy resins, electrical encapsulations