CHAPTER 4

NATURAL AND SYNTHETIC RUBBER

 Introduction
 Elastomer
 The term “elastomer” derived from ‘elastic polymer’
 Polymer that displays elastic properties.
 Rubbery materials.
 Rubber
 The original name given to latex (natural product harvested from the rubber tree).
 The term “rubber” originated from ‘rub away’, because it was used to ‘rub away’ pencil marks.

 Thermoset Elastomer (thermoset rubber)

 Crosslinked rubber
 Undergo a chemical change during processing (vulcanization) to become permanently insoluble
and infusible.
 Thermoplastic Elastomer (TPE)
 Rubbery materials that combine the characteristics of rubber with the recyclability and processing
advantages of plastics.
 Do not required crosslinking
Natural Rubber and Latex
 Natural rubber (NR) is an elastic hydrocarbon polymer that naturally occurs as a milky colloidal
suspension (latex) in the sap of the rubber tree (hevea brasiliensis).
 Natural rubber has elastic properties and it undergoes long range reversible extension even if
relatively small force is applied to it.
 Natural rubber is prepared from latex which is a Colloidal Solution of Rubber in Water.
 Natural rubber is a natural polymer of isoprene (2-Methyl -1, 3 – Butadiene)
 Cis-polyisoprene

Isoprene cis-polyisoprene
 cis-polyisoprene

 Natural rubber (cis-polyisoprene) does not have a straight chain but has a coiled structure. As
a result of this, it gets elastic property.
 stretched

Randomly coiled chains Aligned chains

 NR Latex
 NR latex in Hevea Brasiliensis is located in latex vessels to be founded in various parts of the tree.
 It is obtained from them by tapping based on cutting of the tree bark by special knife under approximate
angle of 30°.
 Natural rubber latex is a colloid system having the rubber particles dispersed in water.
 Small amounts of proteins, resinous matters (including lipids), hydrocarbons and mineral substances
are also present in NR latex.
 Part of these non-rubbery matters, mainly proteins and lipids, is surrounded by a surface of rubbery
particles and gives them negative charge, which assures the latex stability.
 Some rubber products (e.g. foam rubber, gloves, condoms, glues) are produced directly from latex.
 The latex is modified for these reasons to have higher dry rubber content, DRC values (minimum 60 –
65 % of rubber).
 Modification methods: centrifugation, sedimentation, water evaporation thickening and electro-
decantation.
 During this modification process, dry rubber content is increased in latex and impurities and non-
rubbery additives are removed from rubber
Recovering rubber from latex
 The preferred method of recovering rubber from latex involves coagulation - adding an acid such
as formic acid (HCOOH); coagulation takes about 12 hours.
 The coagulum (soft solid slabs) is then squeezed through a series of rolls which drive out most of
the water and reduce thickness to about 3 mm.
 The sheets are then draped over wooden frames and dried in smokehouses for several days.
 Coagulated rubber on separation and drying gives crude (raw) rubber.
 Rubber, at this stage, is soft, sticky and thermoplastic. It has low tensile strength and low
elasticity.
 The properties of rubber can be dramatically altered by crosslinking the polymer chains.
 Vulcanisation process
Vulcanisation process
 Vulcanization (curing, cross-linking) is one of the most important processes for most of
rubber technologies.
 Sulphur vulcanization process was discovered in 1839 by Charles Goodyear in USA.
 Vulcanization of rubbers by sulfur alone is an extremely slow and inefficient process.
 The chemical reaction between sulfur and the Rubber Hydrocarbon occurs mainly at the
C = C (double bonds) and each crosslink requires 40 to 55 sulphur atoms (in the absence
of accelerator). The process takes around 6 hours at 140°C for completion, which is
uneconomical by any production standards.
 Accelerators were invented and became a part of rubber compounding
formulations.
 Accelerator increases the speed of vulcanization and permit
vulcanization to proceed at lower temperature and with greater efficiency.
 It also decreases the quantity of sulphur necessary for vulcanization and
thus improving 'aged' properties of the rubber vulcanizates.

Charles Goodyear
 Vulcanization is a cross linking process in which individual molecules of rubber (polymer) are
converted into a three dimensional network of interconnected polymer chains through
chemical cross links.
 This crosslinking produces a net-like structure that gives a more stable elasticity than the
purely electrostatic nature of the pre-vulcanisation bonds.
 Sulphur, the original crosslinking agent (curative), remains the most successful and
economical cross linking agent even today.
 Sulfur as vulcanizing agent has a limitation. The elastomers must contain chemical
unsaturation (C=C double bonds) for sulfur cross linking.
 Amount of sulphur used for vulcanization process determines the extent of hardness or
toughness of the cured rubber.
 Other chemicals used for cross linking of polymers are Sulfur Monochloride, Tellurium,
Selenium, Thiuram accelerators, Polysulphide polymers, p-Quinonedioximes, Metallic
Oxides, Organic Peroxides, Di-isocyanates, etc.
 The addition of other chemicals and fillers can further enhance the eventual properties of the
finished rubber item.
 Sulphur vulcanization technique comprises the following principal stages:

1. Mixing of crude rubber with about 5-30% of sulfur (cross-linking agent) and other
additives such as:
 activator (commonly zinc oxide or stearic acid)
 accelerator (guanidines, thiazoles, dithiocarbamates, xanthates, thiurams) ,
 coagulants (acetic acid, calcium chloride),
 anti-oxidants (amines, phenolics, phosphites),
 color pigments,
 surfactants,
 softeners (oils),
 anti-foaming agents,
 anti-tack agents (Rosin derivates, coumarone-indene resins, aliphatic
petroleum resins, alkyl-modified phenol-formaldehyde resins).
2. Molding (shaping) the rubber mixture. The rubber must be shaped prior to heating
stage since cross-linking makes shaping impossible.
 Shaping processes for rubber products can be divided into four basic
categories: extrusion, calendering, coating and molding & casting.
3. Heating the mixture to 250-400ºF (120-200ºC). Increased temperature speeds up
the vulcanization process resulting in fast and complete cross-linking. C-S bonds
replace C-H bonds linking chain polyisoprene molecules. Each link is formed by
one to seven sulfur atoms

Calendering Coating of fabric with rubber using a

calendering process
 Properties of rubber improved by vulcanization:
 tensile strength
 Elasticity
 Hardness
 tear strength
 abrasion resistance
 resistance to Solvents.
Natural Rubber chemical
structure after sulphur
vulcanization. Isoprene
molecular chains (CH3) are
crosslinked by sulphur (S)
Difference between Vulcanized rubber and Natural rubber
 Natural rubber is not an important polymer for commercial purpose because of its
softness and tacky (sticky) properties. Softness of natural rubber increases with the
increase in temperature while brittleness increases at low temperature.
 Other properties which decrease the quality of natural rubber are:
o It has large water absorption capacity
o It has low tensile strength & low resistance to abrasion
o It is not – resistant to abrasion
o It is easily attacked by organic reagents.
 The properties of natural rubber is improved by vulcanization process.
 The vulcanized rubber obtained has properties that are just opposite to that of natural
rubber. These properties are
 Vulcanized rubber has excellent elasticity.
 Low water absorption tendency
 It is resistant to the action of organic solvents
 It is resistant to attack of oxidizing agents.
Synthetic Rubber
 Thermoplastic Elastomers (TPE)
 TPE is a thermoplastic polymer that possesses the properties of a rubber.
 TPEs are processed like thermoplastics, but their applications are those of an elastomer.
 Most common shaping processes are injection molding and extrusion, which are
generally more economical and faster than the traditional processes used for rubbers that
must be vulcanized.
 The benefit of using thermoplastic elastomers is the ability to stretch to moderate
elongations and return to its near original shape creating a longer life and better physical
range than other materials.
 Molded products include shoe soles, athletic footwear, and automotive components such
as fender extensions and corner panels.
 Extruded items include insulation coating for electrical wire, tubing for medical
applications, conveyor belts, sheet and film stock.
 Example of TPE: Thermolast, Hipex, Copec, For Tec E, Santoprene, Termoton, Arnitel,
Solprene, Engage, Hytrel, Dryflex, Mediprene, Kraton, and Pibiflex.
 No tires of TPE
 SBS Rubber
 Poly(styrene-butadiene-styrene), or SBS, is a hard rubber that is used to make soles of shoes, tire
treads, and other products where durability is important.
 Polystyrene is a tough hard plastic, and this gives SBS its durability. Polybutadiene is rubbery, and
this gives SBS its rubber-like properties.
 In addition, the polystyrene chains tend to clump together. When one styrene group of one SBS
molecule joins one clump, and the other polystyrene chain of the same SBS molecule joins another
clump, the different clumps become tied together with rubbery polybutadiene chains. This gives the
material the ability to retain its shape after being stretched.

Structure of Poly(styrene-butadiene-styrene)
Trans-polyisoprene

 Synthetic rubber (trans-polyisoprene) was obtained by the free radical polymerization of isoprene.
 The rubber so formed has all trans- Configuration.
 As a result of this, synthetic rubber has a highly regular zig-zag chain which cannot be stretched.
This accounts for non-elasticity of Synthetic Rubber.

Structure of synthetic rubber (trans-polyisoprene)

 Neoprene

 Neoprene or polychloroprene is a synthetic rubber that are produced by polymerization of

chloroprene.
 DuPont marketed polychloroprene as Neoprene, a trademarked name that has since become
generic
 Neoprene is valued for its high tensile strength, resilience, oil and flame resistance, and resistance to
degradation by oxygen and ozone; however, its high cost limits its use to special-properties
applications.
 Neoprene is used in the manufacture of hoses, gaskets, shoe heels, stoppers, conveyor belts and
printing rollers etc. It is also used as an insulator.

Structure of neoprene
 Nitrile rubber (BUNA-N)
 BUNA–N is obtained by copolymerization of 1, 3 – Butadiene and acrylonitrile in presence of a
peroxide catalyst.
 The name BUNA–N is made up of Bu which indicates 1,3 – Butadiene, NA is for Sodium (Na) and N
indicates acrylonitrile.
 BUNA-N is resistant to the action of petrol, lubricating oils and organic solvents.
 It is used in making oil seals, hoses, tank linings etc

1, 3-Butadiene reacts with Acrylonitrile to

produce Buna – N
Natural Rubber and Synthetic
Rubber
Differences
 Differences between natural rubber and synthetic rubber
Natural Rubber
 Extracted from rubber trees and going through
processing of vulcanization.
 High tensile strength and is resistant to fatigue
from wear such as chipping, cutting or tearing.
 Moderate resistance to damage from exposure
to heat, light and the ozone in the air.
 NR has tack, which means it can adhere to
itself as well as other materials. It adheres
particularly well to steel cord, which makes it
an excellent material for use in tires.
Synthetic Rubber
 Made of various monomers after the
polymerization.
 Better resistance to abrasion than natural
rubber, as well as superior resistance to heat
and the effects of aging.
 Many types of synthetic rubber are flame-
resistant, so it can be used as insulation for
electrical devices.
 It also remains flexible at low temperatures and
is resistant to grease and oil.
 Natural Rubber vs Synthetic Rubber

 Overall, the combined properties of natural rubber outweigh synthetic rubbers or

combinations of synthetic rubbers available.
 However, synthetic rubber is advantageous because it is easier to produce.
 Natural rubber is a crop able to grow only in tropical climates and it doesn't age well, so
for many countries it is easier to use synthetic rubber.
 Synthetics may also be more useful in certain applications because of their resistance to
extreme temperatures and corrosive environments.