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Elastomer Technology
PE-4107
Lecture 06,07
Types of Rubbers

Lecture Overview
Introduction of general purpose elastomers
General purpose elastomers
Natural Rubber NR
Classification
Grades of NR
Modified grades of NR
Isoprene IR
Stereospecificity
Polymerization process
Applications

- Comparison of NR and IR

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Introduction

General Purpose Elastomers

These elastomers are widely used in
- Tyres
- Mechanical rubber goods industry
Gaskets

Tear resistant rubber parts

Automobile rubber parts
Conveyor belts
Oil seals

Anti-Vibration Pads
Pump parts

Introduction

General Purpose Elastomers

General purpose elastomers are
-

Natural rubber (NR)

Polyisoprene (IR)
Polybutadiene (BR)
Styrene Butadiene rubber (SBR)
Nitrile Butadiene (NBR) *
Ethylene propylene (EPM and EPDM) *

These rubbers have

-

Good physical properties

Processability
Compatibility
Generally very economical

* Sometimes considered as General Purpose Elastomer

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Introduction

General Purpose Elastomers

For NR, IR, BR compounding, processing and curing are
similar
They all contain unsaturation in their backbones
- Can be vulcanized with sulfur

Zinc oxide and stearic acid are almost always used to activate
organic accelerators

- Crosslinked with peroxides

These polymers all respond well to fillers such as

- Carbon black
- Silica
- Clay

They can be extended with

- Aromatic
- Naphthenic
- Sometimes paraffinic oils

Introduction

General Purpose Elastomers

Due to unsaturation in the backbone
- They are all susceptible to ozone and oxygen attack
- They perform best with the addition of
Antiozonants
Antioxidants

These polymers have good physical properties

including
-

Resistance to abrasion
Tear
Traction (Adhesive friction)
Good low heat build-up

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Introduction

General Purpose Elastomers

These elastomers cannot be used
- In high temperature applications
- Where they come into contact with oils and solvents

Other elastomers can give

-

Lower gas permeability (e.g. butyls and halobutyls)

Better ozone resistance (e.g. EPR and EPDM)
Better solvent resistance (e.g. NBR)
Better heat resistance (e.g. Silicones and fluoro
elastomers)

But none can compete the combination of overall

performance and cost inherent in general purpose
elastomers

General Purpose Elastomers

Natural Rubber and Polyisoprene

Natural rubber and Polyisoprene have the same monomer
chemistry
- Isoprene is the building block of these polymers
- Can polymerize in four different configurations
Cis-1,4
Trans-1,4
Trans-1,2
Trans-3,4

Polyisoprene can be polymerized with

- Coordination catalyst (Ziegler Natta)

At a ratio around 1:1 the Al/Ti system can produce cis contents
from 96-98%

- Alkyl lithium catalyst

Produces cis contents between 90-93%

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Isoprene Configurations

Isoprene Monomer

Cis 1,4

Trans 1,4

Trans 1,2

Trans 3,4

General Purpose Elastomers

Natural Rubber and Polyisoprene

Natural rubber has a cis content of almost 100%
- These microstructure gives natural rubber a glass
transition temperature Tg of approximately -75 0C

Due to the presence of trans-1,2 and 3,4

configurations

- The glass transition temperature is slightly higher Tg -70

to -72 0C

There are three general forms of polyisoprene

commercially available
- High cis contents
It has the ability to undergo strain induced crystallization
This phenomenon gives cis-polyisoprene very high tear strength

Exceptional tear strength translates into superb physical

properties and performance in the end product

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General Purpose Elastomers

Natural Rubber and Polyisoprene

- High trans contents
Gutta-percha or Balata contains high trans content

polyisoprene

It is very hard at room temperature

Upon heating to 80 0C the crystallinity melts and the rubber

becomes soft and workable

- High 3,4-trans contents

Commercially available polyisoprene with 60% 3,4-trans

content

It has the glass transition temperature Tg of about -5 0C

It is processable at normal operating temperatures

For most applications neither high trans nor the high

3,4-trans polymers can match the high cis polymers
for performance

General Purpose Elastomers

Natural Rubber

Present suppliers are Malaysia, Indonesia, Sri Lanka,

Nigeria and others
Production of the natural product begins at the
plantation where a slit is made into the bark of the
rubber tree to allow the flow of a milky sap
The latex consists of
- Water
- Polyisoprene
- Small quantities of other ingredients such as proteins and
carbohydrates

It is collected and coagulated with formic acid in large

tanks

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General Purpose Elastomers

Natural Rubber

Coagulum is squeezed between rollers

- This removes excess water
- The obtained mass is then dried

Much of is then baled and shipped off to the rubber

processor
Some areas of rubber industries use the latex directly
for
Medical gloves
Contraceptive industries

- In this case the latex is concentrated and mixed with

ammonia for mechanical stabilization at the plantation
and shipped out

Natural Rubber
Classification

There are two generic classifications of natural rubber

- Crepe NR

Is a crude form of NR that is characterized by a crinkled texture

Natural rubber in the form of colorless or pale yellow crinkled

sheets prepared by pressing bleached coagulated latex through
corrugated rollers

Used to construct shoe soles

- Sheets

Natural rubber sheets are used in the applications requiring

elasticity and flexibility combined with resistance to abrasion,
tearing and low temperatures

It is tough, organic material that resists alkalis, salts, mild acids

and other types of chemicals

It is common material for tyres and gaskets

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Natural Rubber

Grades of Natural Rubber

Type

Source

Ribbed Smoked Sheet

Coagulated field latex

Pale Crepe

Coagulated field latex

Estate Brown Crepe

Estate cuplump, tree lace

Compo Crepe

Cuplump, tree lace, wet slab, RSS

cuttings

Thin Brown Crepe

Cuplump, tree lace, wet slab, unsmoked

sheet

Thick Brown Crepe

Cuplump, tree lace, wet slab, unsmoked

sheet

Flat Bark Crepe

Cuplump, tree lace, earth scrap

Pure Smoked Blanket Crepe

Remilled RSS and RSS cuttings

Wet slab: Still wet from the coagulation tanks

RSS cutting: Ribbed smoked sheets

Natural Rubber

Grades of Natural Rubber

Technically specified rubbers (TSR)

- Technical specifications suits the requirements of the manufacturing

sector
- TSR include assurance of quality for important technical parameters

Consistency in quality
Minimum space for storage
Clean and easy to handle packing

Different methods are developed to produce TSR all these

processes involves certain common steps such as
-

Coagulation of latex
Processing of field coagulum
Size reduction
Grading

Drying
Baling
Testing
Grading

Difference among commercial processes lie in

- The method of coagulation
- Machinery used for crumbling the coagulum

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Grades of Natural Rubber

Technically Specified Rubber
Nomenclature of TSR in different countries
Country

Nomenclature

Malaysia

Standard Malaysian
Rubber (SMR)

Indonesia

Standard Indonesian
Rubber (SIR)

Thailand

Standard Thai Rubber

(STR)

India

Indian Standard Natural

Rubber (ISNR)

Sri Lanka

Sri Lanka Rubber (SLR)

Singapore

Standard Singapore
Rubber (SSR)

Natural Rubber

Grades of Natural Rubber

Modification of
NR

Physical

Incorporation of
compounding
ingredients

Chemical

Polymer blends
NR/SR,
NR/plastics

Intramolecular
changes

Grafting

Attachment of
functional groups

OENR

TPNR

Cyclization

Styrene

Vulcanization

Masterbatches

Impact modified
plastics

Cis-trans
isomerization

Methyl
Methacrylate

Epoxidation

Depolymerization

Acrylonitrile

Halogenation

Peptization

Maleic anhydride

Hydro
halogenation

Acrylamide

Hydrogenation

Latex stage
compounds

Other forms

Deproteinized NR

Powdered NR

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Natural Rubber

Modified Grades of Natural Rubber

Modified natural rubbers are treated usually performed at
the latex stage. These include
1. Epoxidized Natural Rubber (ENR)
Typical formation of ENR from NR

Cis-1,4-isoprene employing peracetic acid

Isoprene and epoxidized isoprene act as monomer units that are randomly
distributed along polymer chain

Various degree of epoxidation of NR is commercially available

ENR-25 contains 25% of isoprene units

ENR-50 contains 50% of isoprene units
ENR-75 contains 75% of isoprene units

Epoxidation changes several physical properties

Increase in Tg
Higher damping
Lower gas permeability
Increased polarity

This reduces swelling in non-polar oils and increase compatibility with polar
polymers such as Polyvinyl chloride

Damping is an effect that reduces the amplitude of oscillations in an oscillatory system

Natural Rubber

Modified Grades of Natural Rubber

2.

Deproteinized Natural Rubber (DNR)

Natural rubber is treated with proteolytic enzymes that removes the
allergenic protein from fresh natural rubber

3.
4.

Heveaplus MG Rubber

Natural rubber with grafted polymethyl methacrylate side chains

Thermoplastic Natural Rubber (TNR)

Blends of natural rubber and polypropylene

Oil extended natural rubber (OENR)

This contains 20-25 phr of aromatic or naphthalenic oil and is

produced either in

Latex stage or
Dry rubber stage

Increasing oil content reduces tensile strength and resilience

But the vulcanizate retain good tear resistance and possess high wear
resistance when blended with butadiene rubber

OENR shows good skid resistance on wet surfaces when used in

tyre tread

Proteolytic enzymes break the long chainlike molecules of proteins into shorter fragments (Peptides)

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General Purpose Elastomers

Polyisoprene

IR can be polymerized to produce a variety of isomers depending on

the polymerization conditions
These differ in position of the insertion
- 1,2
- 1,4

Exist in cis or trans forms depending on the orientation of the substituents

across the double bond
Cis 1,4-IR is a synthetic analogue of NR
Trans 1,4-IR is a tough semicrystalline polymer

- 3,4

Stereospecific (cis versus trans) and regio specific (1,2 versus 1,4)
catalysts include
- Anionic lithium-alkyl system
- Coordination catalysts similar to Ziegler-Natta catalyst

All synthetic IR elastomers are produced by solution polymerization

using solvents either
- C5-C7 alkanes or
- Aromatic compounds

Polyisoprene
Stereospecificity
Cis 1,4-IR
- Was first made using Ziegler-Natta catalyst consisting of
TiCl4 in conjugation with trialkyl aluminum
- Later Cis 1,4-IR was made by alkali metal polymerization
to give >90% Cis 1,4-IR
- Cis 1,4-IR of predictable molecular weight can also be
prepared by anionic polymerization

Trans 1,4-IR
- Is a thermoplastic
- Is made using Ziegler-Natta catalyst with vanadium as
the transition metal

Mixed (cis/Trans) isomer 1,4-IR

- This is made using free radical emulsion polymerization

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Isoprene Configurations

Isoprene Monomer

Cis 1,4

Trans 1,2

Trans 3,4

Trans 1,4

Polyisoprene

Polymerization Process
Before entering the reactors the solvent, catalyst
and isoprene monomer must be free of catalyst
poison
- Chemical impurities
- Moisture
- Air

Purified stream enter a chain of reactors in series

into which the catalyst is injected and
polymerization begins
At desired extent of polymerization short stop or
catalyst deactivator
Non-staining antioxidant is added to protect the
polymer during finishing and storage
The cement mixture passes the stripping section
which recovers solvent and polymer cement is
converted to crumb by hot water and steam
Crumb slurry passes through extruders to
remove water before it is cooled, baled, packaged
and placed in storage ready for shipment

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General Purpose Elastomers

Uses of Polyisoprene
Trans 1,4-IR
- Crystalline thermoplastic
with a melting point
around 60 0C
- Resists abrasion,
scuffing and cutting
- Application
Mainly used in high

quality golf ball covers

Orthopedic devices
Transmission belts
Cable covering

Cis 1,4-IR

Tyres and Tyre products

Belts and gaskets
Hoses
Foam rubber, molded and mechanical goods
Baby bottle teats, gloves, caulking, sealants, footwear and sporting
goods

Adhesives

Natural Rubber and Polyisoprene

Comparison
Synthetic Polyisoprene
Consists of 99% rubber
hydrocarbons (RHC)
Lighter in color and more
consistent in chemical and
physical properties
Its lower molecular weight leads
to easier processing
- Mw ranges between 755
thousand and 1.25 million
- MWD vary from less than 2.0 for
lithium-catalyzed polyisoprene
to almost 3.0 for Al/Ti-catalyzed
polyisoprene

Natural Rubber
Consists of 93% rubber
hydrocarbons (RHC)
Higher green strength and
modulus
- Especially at higher strain levels
and temperatures

The Mw ranges from 1 million to

2.5 million
- MWD is greater than 3.0 and
widely variable

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