POLYMERS

Characteristics of polymers (plastics)

1. Organic materials

2. Long-chain molecule composed of many “mers” bonded together

3. “mer” is building block of the long-chain (e.g. -C2H4- in polyethylene)

4. Compound of hydrogen and carbon, and/or O, N, F and Si

5. Extensive formability and ductility

6. Light weight, low cost

7. Low strength compared with metals; lower melting point and higher chemical reactivity
compared with ceramics
Definitions

• Polymer: long molecule made up by the repetition of small units

Synonym: macromolecule
High molecular weight (M)
Ex. → polystyrene (PS)

• Monomer: molecule that combines with others (identical or different) to form

a polymer
Ex. → ethylene (PE – polyethylene)

• Oligomer: low molecular weight polymer, constituted of at least two

monomers
Polymers

• Polymers are organic, chain molecules.

• They can vary from a few, to hundreds of thousands of atoms long.

• There are three classes of polymers that we will consider in turn:

– Thermoplastic: flexible linear chains
– Thermosetting: rigid, 3-D networks
– Elastomeric: linear, cross-linked chains
1.The critical feature of a monomer in polymerization:
The presence of reactive sites - double bonds

2. A saturated hydrocarbon - All bonds are single bonds

3. Unsaturated monomer - double or triple covalent bonds.

Polymer

A polymer is a large molecule (macromolecule) composed of repeating structural units connected by covalent chemical
bonds. The word is derived from the Greek words πολσ (poly), meaning "many"; and μέρος (meros), meaning "part". A
simple example is polyethylene or polystyrene whose repeating unit structure is shown.

Polymer synthesis is the process of combining many small molecules known as monomers into a covalently bonded
chain. During the polymerization process, some chemical groups may be lost from each monomer. The distinct piece of
each monomer that is incorporated into the polymer is known as a repeat unit or monomer residue.
The simplest form of polymer molecule is a straight chain or linear polymer, composed of a single main chain. A
branched polymer molecule is composed of a main chain with one or more substituent side chains or branches. If the
polymer contains a side chain that has a different composition or configuration than the main chain, the polymer is called
a graft or grafted polymer. A cross-link suggests a branch point from which four or more distinct chains emanate. A
polymer molecule with a high degree of crosslinking is referred to as a polymer network. Sufficiently high crosslink
concentrations may lead to the formation of an 'infinite network', also known as a 'gel', in which networks of chains are
of unlimited extend - essentially all chains have linked into one molecule.
Polymer Molecules

Before we discuss how the polymer chain molecules are formed,

we need to cover some definitions:

• The ethylene monomer looks like:

• The polyethylene molecule looks like:

• Polyethylene is built up from repeat units or mers.

• Ethylene has an unsaturated bond (the double bond can be

broken to form two single bonds.
• The functionality of a repeat unit is the number of sites at
which new molecules can be attached.
– The functionality of ethylene is 2
 Polymers structures

Schematic representations of (a) linear, (b) branched, (c) crosslinked, and

(d) network (three dimensional) molecule structures.

Circles designate individual mer units.

The geometric arrangement of the bonds is not the only way the structure of a
polymer can vary. A branched polymer is formed when there are "side chains"
attached to a main chain. A simple example of a branched polymer is shown in the
following diagram.

There are, however, many ways a branched polymer can be arranged. One of
these types is called "star-branching". Star branching results when a
polymerization starts with a single monomer and has branches radially outward
from this point. Polymers with a high degree of branching are called dendrimers
Often in these molecules, branches themselves have branches. This tends to give
the molecule an overall spherical shape in three dimensions.
Homopolymers and co-polymers

Homopolymers vs. co-polymers:

-If only one type of repeat unit is present, the polymer is called
a homopolymer.

-If a second monomer is also present in the chain, the resulting

material is called a co-polymer.

Model for a homopolymer:

--X--X--X--X--X--X--X--X--X--X--X—X

Model for an alternating co-polymer:

--X--W--X--W--X--W--X--W--X--W--X—W

Model for a random co-polymer:

--X--X--X--W--X--W--X--X--W--X--W—W

Model for a block co-polymer:

--X--X--X--X--X--X--X--X--W--W--W--W--W--W--
Graft: a polymer is grafted to another preformed macromolecule
Ex → Impact resistant PS
PS branches on polybutadiene (rubber)

Block : long sequences of different repeating units

∼ A-A-A-A-A-A-B-B-B-B-B-B-B-B-B-A-A-A ∼
A separate kind of chain structure arises when more that one type of monomer is
involved in the synthesis reaction. These polymers that incorporate more than one
kind of monomer into their chain are called copolymers. There are three important
types of copolymers. A random copolymer contains a random arrangement of the
multiple monomers. A block copolymer contains blocks of monomers of the same
type. Finally, a graft copolymer contains a main chain polymer consisting of one
type of monomer with branches made up of other monomers. The following diagram
displays the different types of copolymers.

Random
Block Copolymer Graft Copolymer
Copolymer
An example of a common copolymer is Nylon. Nylon is an alternating copolymer
with 2 monomers, a 6 carbon diacid and a 6 carbon diamine. The following picture
shows one monomer of the diacid combined with one monomer of the diamine:
Copolymer
Configuration
The two types of polymer configurations are cis and trans. These structures can not be changed by physical means
(e.g. rotation). The cis configuration arises when substituent groups are on the same side of a carbon-carbon double
bond. Trans refers to the substituents on opposite sides of the double bond.

Stereoregularity is the term used to describe the configuration of polymer chains. Three distinct structures can be
obtained. Isotactic is an arrangement where all substituents are on the same side of the polymer chain. A syndiotactic
polymer chain is composed of alternating groups and atactic is a random combination of the groups. The following
diagram shows two of the three stereoisomers of polymer chain.

Isotactic Syndiotactic
cis-1,2-dichloroethene (left); trans-1,2-dichloroethene (right)
Cis-trans isomerism
In stereoisomerism, the atoms making up the isomers are joined up in the same order, but still manage to have a different
spatial arrangement. Geometric isomerism is one form of stereoisomerism.
In one, the two chlorine atoms are locked on opposite sides of the double bond. This is known as the trans isomer. (trans :
from latin meaning "across" - as in transatlantic).
In the other, the two chlorine atoms are locked on the same side of the double bond. This is know as the cis isomer. (cis :
from latin meaning "on this side")

The most likely example of geometric isomerism you will meet at an introductory level is but-2-ene. In one case, the CH3 groups
are on opposite sides of the double bond, and in the other case they are on the same side.

In chemistry, cis-trans isomerism or geometric isomerism or configuration isomerism is a form of stereoisomerism

describing the orientation of functional groups within a molecule. In general, such isomers contain double bonds, which cannot
rotate, but they can also arise from ring structures, wherein the rotation of bonds is greatly restricted.
Tacticity
Tacticity (from Greek 'taktikos': of or relating to arrangement or order) is the relative stereochemistry within a macromolecule.
Stereochemistry is a subdiscipline of chemistry, involves the study of the relative spatial arrangement of atoms within molecules.
The practical significance of tacticity rests in the link between tacticity and the physical properties of the polymer. The regularity
of the macromolecular structure influences the degree to which it has rigid, crystalline long range order or flexible, amorphous
long range disorder. Precise knowledge of tacticity of a polymer also helps understanding at what temperature a polymer melts,
how soluble it is in a solvent and its mechanical properties.
Isotactic polymers
Isotactic polymers are composed of isotactic macromolecules (IUPAC definition). In isotactic macromolecules all the
substituents are located on the same side of the macromolecular backbone

Syndiotactic polymers
In syndiotactic or syntactic macromolecules the substituents have alternate positions along the chain.

Atactic polymers
In atactic macromolecules the substituents are placed randomly along the chain.

Polymers that are formed by free-radical mechanisms such as polyvinylchloride are usually atactic. Due to their random nature
atactic polymers are usually amorphous.
Atactic polymers are technologically very important. A good example is polystyrene (PS). Most industrial polystyrene produced is
atactic.
Chain length
Polymer bulk properties may be strongly dependent on the size of the polymer chain. Like any molecule, a polymer
molecule's size may be described in terms of molecular weight or mass. In polymers, however, the molecular mass may
be expressed in terms of degree of polymerization, essentially the number of monomer units which comprise the polymer.
For synthetic polymers, the molecular weight is expressed statistically to describe the distribution of molecular weights in
the sample. This is because of the fact that almost all industrial processes produce a distribution of polymer chain sizes.
Examples of such statistics include the number average molecular weight and weight average molecular weight.

Glass transition temperature

A parameter of particular interest in synthetic polymer manufacturing is the glass transition temperature (Tg), which
describes the temperature at which amorphous polymers undergo a second order phase transition from a rubbery, viscous
amorphous solid to a brittle, glassy amorphous solid. The glass transition temperature may be engineered by altering the
degree of branching or cross-linking in the polymer or by the addition of plasticizer.

Chemical cross-linking
Cross linking tends to increase Tg and increase strength and toughness. Cross linking consists of the formation of
chemical bonds between chains. Among other applications, this process is used to strengthen rubbers in a process known
as vulcanization, which is based on cross linking by sulphur. Car tires, for example, are highly cross linked in order to
reduce the leaking of air out of the tire and to toughen their durability. Eraser rubber, on the other hand, is not cross linked
to allow flaking of the rubber and prevent damage.
Thermoplastic polymers

1. Become soft and deformable upon heating

2. Linear polymers including those that are branched but not cross-linked

3. High-temperature plasticity – due to the ability of the molecules to slide

past one another (thermally activated)

4. The ductility of thermoplastic polymers is reduced upon cooling

Thermosetting polymers

1. Becoming hard and rigid upon heating, the opposite of thermoplastics

2. This phenomenon is not lost upon cooling

3. With network molecule structure, formed by the step-growth mechanism,

the chemical reaction are enhanced by high temperatures and are
irreversible

4. Thermosets with significant strength and stiffness

Being common metal substitutes
Not being recyclable
Additives

Plasticizer
To soften a polymer
Blending with a low-molecular-weight polymer

Filler
To strengthen a polymer by restricting chain mobility
Inert materials are used, e.g. short-fiber cellulose and asbestos, carbon black

Stabilizers
To reduce polymer degradation, e.g. To retard the room temperature oxidation by
adding complex phenol group

Flame retardants
To reduce the inherent combustibility
Halogens e.g. Cl atoms, by terminating free-radical chain reaction

Colorants
To provide colour to a polymer
Pigments (insoluble), and dyes (soluble and provide transparent colour)
 Plastics - or polymers - fall into two main groups: Thermo and Thermoset plastics, a third group is called Elastomers.

Thermoplastics can be made 'plastic' and malleable at high temperatures. Modern thermo plastic polymers melt any
where between 65 degrees C and 200+ degrees C. In this state they can be moulded in a number of ways: They differ
from thermo set plastics in that they can be returned to this plastic state by reheating. They are then fully recyclable.
Thermo plastics include:

Properties Applications and Uses

Name
ABS- Acrylonitrile-butadiestryrene Strong, tough, hard, chemical resistant, durable. All Dash boards and car trim, toys, phones,
process. handles, electrical products.

Nylon ( polyamide) Tough, hard, light, self lubricating, chemical resistant, Bearings, gears, rope, hinges and catches,
machines well, extrudable, injects well. engineering applications.

Acetate - cellulose Tough stiff and hard, transparent and light, heat Tool handles, pen bodies, frames for
resistant. glasses. Can be injection moulded.

Acrylic- polymethlacrilate stiff, durable, insulator, machines well, polishes well Car light covers, baths, shower trays,
scratches easily basins. can be line bent/vac
formed/injection moulded with ease.

Polypropylene Tough, light, chemical resistant.. Will scratch, quite soft. Containers, pots, plastic seats, ropes, nets.
Very versatile.

Polystyrene light, stiff, transparent, brittle, waterproof/resistant. toys, electrical product cases, boxes
expanded- very light packaging
high impact- very tough vacuum formings

Polythene Tough, flexible, soft, insulator, chemical resistant. Packaging, bags,

Low density Hard, stiff.
High density tube, bottles, domestic appliances.

PVC- Polyvinyl chloride cables and hoses sheet fabric

uPVC Stiff hard tough light Gutters windows extrusions
Thermoset plastics differ in that they are not re-mouldable. Strong cross links are formed during the initial moulding
process that give the material a stable structure. They are more likely to be used in situations where thermal stability
is required. They tend to lack tensile strength and can be brittle.

Name Properties Applications and Uses

Urea formaldehyde Strong, insulator, brittle, hard, stiff. Electrical fittings. Handles
and knobs
Polyester resin Liquid raw state, stiff hard, insulator, chemical resistance, brittle Casting, bonding fibres-
without fibre reinforcement. glass, Kevlar, carbon fibre.
Epoxy resins-trade names include araldite. Good insulator, brittle chemical resistant. adhesives, bonding fibres,
encapsulation.
Melamine formaldehyde Hard, strong, heat resistant. adhesives, bonding fibres,
encapsulation.

Elastomers are a small group of polymers that display stretching and deforming at room temperatures- elastic and
rubbers are examples of this group.

Additives are used in both forms of plastic. These can include:

Stabilisers to prevent degradation due to moisture or UV light.
Lubricants such as sulphides and waxes to make the polymer easier to form and self lubricating in use.
Pigments - often referred to as 'master batch' adding colours to the plastic.
Plasticisers - added to make the plastic less hard or brittle
Fillers - these can be added to enhance properties such as wear/strength/toughness/durability and talc and clay may be
used to bulk out the plastic reducing costs.
Flame retardants - to prevent combustion in materials such as domestic foams.
Blowing agents - to permit foams to be blown.
Anti-static agents - used to prevent the build up of electrical charge.
Two distinct ways for the process of polymerization

1. Chain growth (addition polymerization)

Rapid chain reaction

2. Step growth (condensation polymerization)

Chemical reaction between pairs of reactive monomers
Much slower
Chain growth
 Addition polymerization
Below is an example of how a free radical forms (this one starts with peroxide, HOOH):
The peroxide molecule has an easy-to-break O-O single bond. Heat or light energy can break this O-O single bond.

The single dot represents one electron from the O-O peroxide bond. The HO· fragments are the free radicals, and they are
very unstable and reactive.

Free radicals are very reactive. When a free radical gets close to a double bond, one of the bonds is disrupted. One of the
electrons in the double bond is attracted to the free radical. The double bond breaks, and a new single bond is formed.

Notice that in forming this bond, one electron from the double bond is left alone. Thus, another (larger) free radical has been
formed.

In Summary:

The double bond is a great place for a reaction to occur. The electrons are available here to make new bonds. Reactive
species disrupt the double bond. We have seen a free radical attack a double bond.By the way, we say that the free radical
adds to the double bond.This is Addition polymerization.
The Mechanism of Addition Polymerization
The formation of a polymer by addition polymerization is an example of a chain reaction. Once a chain reaction gets
started, it is able to keep itself going. The three steps of this reaction to focus on are

how the reaction gets started (INITIATION)

how the reaction keeps going

(PROPAGATION)
how the reaction stops (TERMINATION)

I. INITIATION
--- How the reaction gets started ---
A peroxide molecule breaks up into two reactive free radicals. Light or heat can provide the energy needed for
this process.
We can write an equation for this process:

The second part of initiation occurs when the free radical initiator attacks and attaches to a monomer molecule. This forms
a new free radical, which is called the activated monomer.
We can write an equation for this process, too:
II. PROPAGATION
--- How the reaction keeps going ---
During a chain reaction, most of the time is spent in the propagation phase as the polymer chain grows. In the
propagation phase, the newly-formed activated monomer attacks and attaches to the double bond of another monomer
molecule. This addition occurs again and again to make the long polymer chain. )

Once again, we can write an equation for this reaction:

The "n" stands for any number of monomer molecules, typically in the thousands.

III. TERMINATION
--- How the reaction stops ---
This chain reaction cannot go on forever. The reaction must terminate. A growing polymer chain joins with another free
radical. We watched a peroxide break up to form two radicals. It makes sense that two free radicals could join to make a
stable bond.
The equation representing this step of the chain reaction can be written simply as:

Remember: The R and R' groups here can be the original free radicals, the growing polymer chains, or even one
of each. Termination reactions can, however, be more complicated looking.
Chemists can control the way a polymer does each of these steps by varying the reactants, the reaction times, and
the reaction conditions.
The physical properties of a polymer chain depend on the polymer's average length, the amount of branching,
and the constituent monomers.
Step growth (condensation polymerization)
Polymerization techniques

Bulk Polymerization

It is the simplest technique and gives the highest purity polymer. The advantages are high yield per reactor volume, easy
polymer recovery and the option of casting the polymerization mixture into final product form (i.e. cast polymerization).
The limitations are the difficulty of removing the last traces of monomer and the problem of dissipating the heat produced
during polymerization. Increase in temperature increases the polymerization rate but generates additional heat to dissipate.
Near the end of polymerization when viscosity is high, heat removal becomes difficult. Increase in rate of polymerization
means increase in radical concentration. Diffusion of small monomer molecules to the propagation sites become easier. In
other words, termination rate decreases more rapidly than the propagation rate and the overall polymerization rate
increases with accompanying additional heat production. This auto-acceleration process is called the Trommsdorff or gel
effect. Heat dissipation may be improved by providing special baffles or by performing bulk polymerization in separate
steps of low to moderate conversion. Polystyrene, poly(methyl methacrylate) are bulk polymerized for demand of cast
polymerization. LDPE is also produced in this method.

Solution Polymerization

Heat removal during polymerization can be facilitated by conducting the polymerization in an organic solvent or water.
The requirements for selection of the solvent are both the initiator and the monomer be soluble in it. The solvent should
have suitable melting and boiling points for the conditions of polymerization and subsequent solvent-removal step. Other
factors include flash point, cost and toxicity. Examples of solvents are aliphatic and aromatic hydrocarbons, esters, ethers
and alcohols. Solvent reflux may be done to maximize heat removal. The disadvantages are small yield per reactor volume
and the requirement of a separate solvent-recovery step.

Water soluble polymers like poly(acrylic acid), polyacrylamide, PVA etc. can be prepared in aqueous solution. PMMA,
PS, polybutadiene, PVC etc. can be polymerized in organic solvents.
Suspension polymerization

Improved heat transfer can be obtained by using the excellent thermal properties of water through either suspension or
emulsion polymerization. In suspension polymerization, a batch reactor fitted with a mechanical agitator is charged
with a water–insoluble monomer and initiator. Droplets of monomer containing the initiator are formed. These are
typically 50-200 µm in diameter and serve as miniature reactors for the polymerization Coalescence of these sticky
droplets is prevented by the addition of a protective colloid, typically PVA and by constant agitation of the polymer
mixture. Near the end of polymerization, the particles harden and then can be recovered by filtration followed by a
final washing step. Polymer purity is low due to the presence of suspending and other stabilizing additives that are
difficult to remove completely. Extrusion and injection-moulding grades of PVC, poly(styrene-co-acrylonitrile) etc. are
made by this process.

Emulsion polymerization

In addition to water and monomer, the reactor charge consists of a water-soluble initiator and a surfactant such as the
sodium salt of a long-chain fatty acid. The (hydrophobic) monomer molecules form large droplets (0.5 to 10µm in
diameter) which are stabilized by the surfactant molecules. The size of monomer droplets depends upon the
polymerization temperature and the rate of agitation. Above a certain surfactant concentration, the critical miscelle
concentration, residual surfactant molecules can align to form miscelles which are small rod-like structure which
contain 50 to 100 surfactant molecules.
Polyethylene
Polyethylene or polythene (IUPAC name poly(ethene)) is a thermoplastic commodity heavily used in consumer products
(notably the plastic shopping bag). Over 60 million tons of the material are produced worldwide every year. Polyethylene
is a polymer consisting of long chains of the monomer ethylene (IUPAC name ethene).

HDPE is defined by a density of greater or equal to 0.941 g/cm3. HDPE has a low degree of branching and thus stronger
intermolecular forces and tensile strength. HDPE can be produced by chromium/silica catalysts, Ziegler-Natta catalysts or
metallocene catalysts. The lack of branching is ensured by an appropriate choice of catalyst (for example, chromium
catalysts or Ziegler-Natta catalysts) and reaction conditions. HDPE is used in products and packaging such as milk jugs,
detergent bottles, margarine tubs, garbage containers and water pipes.

LLDPE is defined by a density range of 0.915–0.925 g/cm3. LLDPE is a substantially linear polymer with significant
numbers of short branches, commonly made by copolymerization of ethylene with short-chain alpha-olefins (for example,
1-butene,1-hexene and 1-octene). LLDPE has higher tensile strength than LDPE, it exhibits higher impact and puncture
resistance than LDPE. Lower thickness (gauge) films can be blown, compared with LDPE, with better environmental
stress cracking resistance but is not as easy to process. LLDPE is used in packaging, particularly film for bags and sheets.
Lower thickness may be used compared to LDPE. Its applications include cable covering, toys, lids, buckets, containers
and pipe. While other applications are available, LLDPE is used predominantly in film applications due to its toughness,
flexibility and relative transparency.

LDPE is defined by a density range of 0.910–0.940 g/cm3. LDPE has a high degree of short and long chain branching,
which means that the chains do not pack into the crystal structure as well. It has, therefore, less strong intermolecular
forces. This results in a lower tensile strength and increased ductility. LDPE is created by free radical polymerization. The
high degree of branching with long chains gives molten LDPE unique and desirable flow properties. LDPE is used for
both rigid containers and plastic film applications such as plastic bags and film wrap.
HIGH PRESSURE POLYETHYLENE (LDPE)
Polymer grade ethylene (99.9%) mixed with 600 –800 ppm oxygen is compressed in two stages C1 and C2 (50 bars and
3000 bars). The compressed gas is passed into a tube-in-tube type reactor. The incoming gas is heated by outgoing
mixture. Circulation of hot water or dowtherm helps to maintain the temperature. The temperature of the reactants in the
entering zone is around 1500C and it reaches 2400C at the end of the coil. The temperature of the reactor outlet should
never drop below 2000C, as the crystallisation of polyethylene begins, giving obstruction to flow. The reactor products
are passed into high pressure separator (2). The gas obtained from the separator, after purification, goes directly into
second stage compressor (C2). From the high pressure separator the melt goes into a second stage separator (low
pressure) (3), where the remaining ethylene is expelled and routed to first stage compressor C1, through purification
system. In fact, after high pressure separator, there may be a series of cyclones to catch polymer dust. The gases are rich
with ethylene and oxygen, but contain some amount of carbon dioxide and formaldehyde, hence purification is essential
before the gas enters second stage compression. Adequate safety system is desirable while handling such high pressure
gas to actuate exit automatically, if disturbance or flow obstruction appears in the reactor. As high as 80% ethylene is
recycled due to low conversions per pass. LDPE is collected from LP and HP separators.
HIGH DENSITY POLYETHYLENE : ZIEGLER PROCESS
Karl Ziegler developed a composite catalyst system for polymerising ethylene at low pressure and low temperature
(atmospheric pressure and 600C). The composite catalyst is formed by reacting trialkyl aluminium and titanium
tetrachloride. The ratio between ethyl aluminium and titanium tetrachloride is significant in determining the size of
polymer. The ratio is usually kept between 1:1 To 1:1.2. This delivers a molecular mass of 70,000 to more than a lakh.
By increasing the ratio of alkyl aluminium to halide, a polymer of higher molecular weights (a million) are likely.
In the catalyst vessel (1) a fresh and dilute solution composite catalyst (max 0.1 gm/lit) in pentane or hexane is made and
the vessel acts as a reservoir too. The solution is fed continuously into reactor (2) where solvent and ethylene streams
enter. A stirrer is used to homogenise the mixture. The polymer mixture after reaction is allowed to enter a flasher (3)
where unreacted monomer and inerts are vented out. The solid material is given a thorough wash (4) with water to
decompose the catalyst. The strippers (6 & 7) separate the organic solvent from water-hydrocarbon azeotrope and the
solvent is recycled. The polymer material is washed many times, either with water or with methanol, after which it is
filtered (5) and dried. Catalyst is obtained in a slurry and is recovered (8) for usage. Additives for preserving the quality
of polymer are added at the stage of granulation. It is found that by alcoholic wash, the ash content of polymer decreases
very much (i.e. the catalyst removal from the polymer becomes better with alcoholic wash). Before start of the operation
all units are subjected to nitrogen breathing to ensure absence of water or air.
SOLVAY HDPE PROCESS
The catalysts are formed by reacting transition metal compound (TiCl4) with alkyl aluminium (ethyl, propyl, butyl).
Polymerisation is carried out in a loop-type reactor using n-hexane as diluent. Reactor conditions are moderate, 25-35
bars and 50-900C. The resultant slurry is centrifuged. Wide range of molecular weights are possible with this process.
The reactor is tubular and provided with a jacket for circulating cold water. Copolymerisation is possible in this reactor
with co-monomer feed and presence of hydrogen to control the copolymerisation .Polymer fluff is available in hexane
slurry. A depressuriser flash vessel is provided to separate the unreacted reactants for circulation.

LLDPE
LDPE is a linear branched homopolymer of ethylene produced by high pressure free radical polymerization. LLDPE is a
copolymer of ethylene, in which branches are provided by butene-1, hexene-1 or octene-1. It is a random polymer,
having more short chains with no further branching, thus differing from LDPE which has fewer but longer and widely
branched chains. Its physical properties lie between LDPE and HDPE. LLDPE is consumed in a major proportion as a
blend of 30:70 or 50:50 with HDPE.
In the high pressure process, the reaction takes place under supercritical conditions whereby the homogeneous gas phase
behaves like a liquid. The temperature is between 130-2800C and pressure 1500 to 3500 bars. The reaction time lasts 60
to 300 seconds.
Polypropylene
Polypropylene

Polypropylene or polypropene (PP) is a thermoplastic polymer, made by the chemical

industry and used in a wide variety of applications, including packaging, textiles (e.g., ropes,
thermal underwear and carpets), stationery, plastic parts and reusable containers of various
types, laboratory equipment, loudspeakers, automotive components, and polymer banknotes.
An addition polymer made from the monomer propylene, it is rugged and unusually resistant
to many chemical solvents, bases and acids. Melt processing of polypropylene can be achieved
via extrusion and molding.

Chemical and physical properties

Most commercial polypropylene is isotactic and has an intermediate level of crystallinity

between that of low density polyethylene (LDPE) and high density polyethylene (HDPE); PP
can be made both tough and flexible, even at low temperatures. Polypropylene is rugged, often
somewhat stiffer than some other plastics, reasonably economical, and can be made
translucent when uncolored but is not as readily made transparent as polystyrene, acrylic or
certain other plastics. It can also be made opaque and/or have many kinds of colors through
the use of pigments. Polypropylene has very good resistance to fatigue, so that most plastic
living hinges, such as those on flip-top bottles, are made from this material.
Synthesis

Like most other vinyl polymers, useful polypropylene cannot be made by radical polymerization due to
the higher reactivity of the allylic hydrogen (leading to dimerization) during polymerization. Moreover,
the material that would result from such a process would have methyl groups arranged randomly, so called
atactic PP. The lack of long-range order prevents any crystallinity in such a material, giving an amorphous
material with very little strength.

A Ziegler-Natta catalyst is able to limit incoming monomers to a specific orientation, only adding them to
the polymer chain if they face the right direction. Most commercially available polypropylene is made
with such Ziegler-Natta catalysts, which produce mostly isotactic polypropylene. With the methyl group
consistently on one side, such molecules tend to coil into a helical shape; these helices then line up next to
one another to form the crystals that give commercial polypropylene many of its desirable properties.

Uses

A common application for polypropylene is as Biaxially Oriented polypropylene (BOPP). These BOPP
sheets are used to make a wide variety of materials including clear bags. When polypropylene is biaxially
oriented, it becomes crystal clear and serves as an excellent packaging material for artistic and retail
products. In India, polypropylene is used in manufacturing mats to be used at home. Polypropylene is also
used as an alternative to polyvinyl chloride (PVC) as insulation for electrical cables. This is because it
emits less smoke and no toxic halogens, which may lead to production of acid in high temperature
conditions.
Polypropylene is most commonly used for plastic moldings where it is injected into a mold while molten,
forming complex shapes at relatively low cost and high volume, examples include bottle tops, bottles and
fittings.
POLYPROPYLENE
The reaction is carried out at 10-20 bars in the temperature range of 65 to 700C. Polymerisation is done in a medium for
which a solvent is chosen to act either as solvent or medium for slurry. Solvents like heptane or gasolene with no
unsaturates is preferred. Propylene of very high grade purity (99.9%) is essential.

A10% solution of composite catalyst is made in a solvent, usually heptane, and kept in a tank (1).The solution is
proportionally charged into reactor (2),where olefin & some more solvent are admitted .The reactor is kept under
required pressure & temp for about 3-4 hrs to complete the reaction .Feed gas & catalyst thoroughly mix due to agitation
.After the reaction the products are transferred into a stabilizer (3) where pressure is decreased ,to let off unreacted gas
.The catalyst is decomposed by means of alcohol .All the polymer product is centrifuged (4) & the solvent-alcohol
mixture is separated by steam stripping in a striper (5). Recovered solvent is distilled for purification & then to begin
circulation .A separate stripper purifier section is required for this .The heavy polymer with adhering solvent is stripped
in another stripper (6) by means of steam ,& the recovered solvent mixture is processed for alcohol & solvent in section
(7) .Polypropylene collected from the bottom of the stripper (6) is further centrifuged, mixed with stabilisers & sent to
storage .Polypropylene requires about 1.1 tonnes of monomer for each ton of the polymer.
Bi-axially oriented polypropylene film (BOPP) is produced by orienting long chain molecules in two directions .
Polystyrene
Polystyrene is an aromatic polymer made from the aromatic monomer styrene, a liquid
hydrocarbon that is commercially manufactured from petroleum by the chemical industry.
Polystyrene is a thermoplastic substance, normally existing in solid state at room
temperature, but melting if heated (for molding or extrusion), and becoming solid again
when cooling off.

Pure solid polystyrene is a colorless, hard plastic with limited flexibility. It can be cast into
molds with fine detail. Polystyrene can be transparent or can be made to take on various
colours.

Polystyrene is about as strong as unalloyed aluminium, but much more flexible.

Polystyrene's most common use is as expanded polystyrene (EPS). Expanded polystyrene is

produced from a mixture of about 90-95% polystyrene and 5-10% gaseous blowing agent,
most commonly pentane or carbon dioxide. The solid plastic is expanded into a foam
through the use of heat, usually steam.
Poly vinyl Chloride
Polyvinyl chloride, (Polychloroethene) commonly abbreviated PVC, is a widely used
thermoplastic polymer. As a building material, PVC is cheap, durable, and easy to assemble.
In recent years, PVC has been replacing traditional building materials such as wood,
concrete and clay in many areas. The use of non-PVC materials has been on the rise due to
concerns about the environmental and toxicity characteristics of PVC.

Polyvinyl chloride is used in a variety of applications. As a hard plastic, it is used as vinyl

siding, magnetic stripe cards, window profiles, gramophone records (which is the source of
the term vinyl records), pipe, plumbing and conduit fixtures. The material is often used in
Plastic Pressure Pipe Systems for pipelines in the water and sewer industries because of its
inexpensive nature and flexibility.

It can be made softer and more flexible by the addition of plasticizers, the most widely-used
being phthalates. In this form, it is used in clothing and upholstery, and to make flexible
hoses and tubing, flooring, to roofing membranes, and electrical cable insulation.

Polyvinyl chloride is produced by polymerization of the monomer vinyl chloride. Since

about 57% of its mass is chlorine, creating a given mass of PVC requires less petroleum than
many other polymers.

PVC is commonly used as the insulation on electric wires; the plastic used for this purpose
needs to be plasticized.
In a fire, PVC-coated wires can form HCl fumes; the chlorine serves to scavenge free
radicals and is the source of the material's fire retardance. While HCl fumes can also pose a
health hazard in their own right, HCl dissolves in moisture and breaks down onto surfaces,
particularly in areas where the air is cool enough to breathe, and is not available for
inhalation. Frequently in applications where smoke is a major hazard (notably in tunnels)
PVC-free LSOH (low-smoke, zero-halogen) cable insulation is preferred. PVC insulation
may be eaten or degraded by mice, termites, antechinus and cockatoos.

Polyvinyl chloride is also widely used for producing pipes. In the water distribution market
it accounts for 66 percent of the market in the US, and in sanitary sewer pipe applications, it
accounts for 75 percent. Its light weight, high strength, and low reactivity make it
particularly well-suited to this purpose. In addition, PVC pipes can be fused together using
various solvent cements, creating permanent joints that are virtually impervious to leakage.
Despite PVC's many advantages, in cases where very high strength or ease of disassembly
is necessary, metal pipes are still preferred.
POLY VINYL CHLORIDE:
Two types of homopolymers are produced ,one being flexible and the other, a rigid type. Rigid polymers are suitable for
making articles of hard type sheets, papers, gears etc .It is white ,amorphous solid, soluble in chlorinated solvent further,
it is very easily welded at 200oC with rods made of PVC. PVC with 10% acrylonitrile co-polymers dissolves in acetone,
which when spun, yields flame resisting fibre. PVC is made by emulsion polymerisation .The monomer is dispersed in
water which is emulsified with surface acting agents like ammonium salts higher fatty acids, sulphonates, palmitates and
stearates. Water soluble initiator, like ammonium per sulfate is also added to aqueous phase along with a buffer to
maintain pH around 4.
Aqueous phase consisting of emulsifying agent with soluble initiators and buffers is charged into an autoclave. VCM is
discharged into the emulsion in droplets (1m) at 200-1000 KN/m2 pr and the temp is kept as low as possible. The
reaction goes on for 6hrs. Unpolymerised material & latex containing 35-40% polymer are later discharged into
coagulator, where electrolytes coagulates the polymer from latex. The solvent is stripped off from the polymer & the
polymer is then washed, filtered & dried. Autoclaves are cooled to remove the polymer heat by cold water. After the
reaction is over the contents are degassed, unreacted monomer is purified & recycled . Polymer is separated by
centrifugation. Lower temps give rise to high molecular wt. polymer.
Polyethylene terephthalate
The raw materials to make PET are monoethylene glycol (MEG) and purified terephthalic acid (PTA) or dimethyl
terephthalate (DMT). The main process steps are raw material preparation, esterification/transesterification, pre-
polycondensation and polycondensation.

Terephthalic Acid (PTA) is produced directly from p-xylene with bromide-controlled oxidation. The PTA is mixed with
the MEG and catalyst solution in a paste and fed into the esterification system. The esterification takes place under
atmospheric pressure by splitting off the water. Dimethyl Terephthalate (DMT) is made in the early stages by
esterification of terephthalic acid. Ethylene Glycol (EG) is initially generated as an intermediate product by oxidation of
ethylene. Further ethylene glycol is obtained by reaction of ethylene oxide with water.

When DMT is used, the DMT melt and catalyst are pumped with MEG into the transesterification system, where the
reaction takes place under atmospheric pressure by splitting off the methanol. The materials split off are rectified and
recovered.

The product from the esterification/transesterification step is then sent to the pre-polycondensation unit where the
reaction takes place under a vacuum. The pre-polycondensation product is fed to the final polycondensation reactor
which operates under increased temperature and vacuum. The polyester melt is processed either into fibres/filaments or
sent to the solid state polycondensation (SSP) unit to make bottle grade chips.

The majority of the world's PET production is for synthetic fibers (in excess of 60%) with bottle production accounting
for around 30% of global demand. In discussing textile applications, PET is generally referred to as simply "polyester"
while "PET" is used most often to refer to packaging applications.

It is a thermoplastic polyester used for fibre applications, bottles and thermoformed trays, films (magnetic recording
tapes and photographic films). PET can be easily recycled although recycled PET cannot be used for beverage bottles, it
can be used in the manufacture of insulation boards or can be thermally or chemically decomposed to its monomers
which can be used for the polymerization of virgin resin.
 Preparation of PET monomers
Formation of ethylene glycol
OH OH
O2 O
H2C CH2 H3C CH CH CH3
Ag

Formation of TA and DMT

O OH
C H3 C

[ O2 ]

C H3 C
C H OH O OH
C H 3 OH / C o O2 3
TA
O OC H3
C

C
O OC H3

D MT
 PET Polymerization Reactions
Step Growth Polymerization - Condensation O O
O O high Temp
n C C n HO CH2 CH2 OH C C O CH2 CH2 O
-H2O
HO OH n

Ester Interchange - Transesterification

O O
n CH3O C C OCH3 2n HO CH2 CH2 OH

low Temp - 2n CH3OH

O O
HO CH2 CH2 O C C O CH2 CH2 OH

O O
C C O CH2 CH2 O
n
Compression Moulding
• Both thermoplastics and thermosets
can be formed by compression mould
• The polymer, or mixture of resin and
hardener is heated and
compressed between dies
• This method is well suited to
forming of:
– thermoset casings for
appliances
– thermoplastic car bumpers
• Since a thermoset can be
removed when hot, cycle times
can be as low as:
– 10 seconds for small
components
– 10 minutes for large thick
walled mouldings
 Injection Moulding

• In injection moulding, polymer granules are

– compressed by a ram or a screw
– heated until molten
– injected into a cold, split mould under pressure
• The moulded polymer is cooled below Tg
– the mould opens and the product is ejected
• This process gives high precision mouldings because the
polymer cools under pressure
• Cycle time is typically between 1 – 5minutes
Thermoplastic Extrusion
Blow Moulding

The parison is a hollow

tube of softened
plastic It’s shape is
determined
by the screw speed
and/or the die opening
Spinning of polymers
The polymers of synthetic fibers are almost always derived from by-products of petroleum
and natural gas which include nylon, polyethylene terephthalate, as well as other
compounds like acrylics, polyurethanes and polypropylene. Synthetic fibers, which are
produced from these polymers, are used for making various consumer and industrial textile
products ranging from clothing, home furnishings to conveyor belts. Most of the
cellulosic yarns manufactured from synthetic fibers are produced by extrusion of a thick,
viscous liquid through the tiny holes of an equipment called spinneret which forms
continuous filaments of semi-solid polymer

The polymer is at first converted into a fluid state. If it is a thermoplastic polymer then it is just melted
otherwise it has to be dissolved in a solvent or has to be chemically treated in order to form soluble or
thermoplastic derivatives. The fluid polymer is then forced through the spinneret. The polymer here
cools to a rubbery state, and then finally solidifies. There are typically four types of spinning for
polymers-wet spinning, dry spinning, melt spinning, and gel spinning. However, before proceeding to
know the actual processes of all these four types of spinning, one must know about the basic process of
extrusion and the spinneret used for it.
Spinneret and Extrusion
The spinnerets used for manufacturing most of the synthetic fibers have many holes
ranging from one to several hundred holes which gives it an appearance similar to that
of a bathroom shower head. The fluid polymer is fed into these tiny openings. The
liquid polymer emerging out of the holes of spinneret in the form of filaments, is
converted first to a rubbery state and then into a solid state. This process of extrusion
and solidification of innumerable filaments is called spinning of polymers.
Types of Polymer Spinning Processes
There are four types of spinning for polymers- wet spinning, dry spinning, melt spinning, and gel
spinning.

Wet Spinning: Of all the four processes, wet spinning is the oldest process. It is used for polymers that
need to be dissolved in a solvent to be spun. The spinneret remains submerged in a chemical bath that
leads the fiber to precipitate, and then solidify, as it emerges out of the spinneret holes. The name of the
process i.e. wet spinning has got its name from this "wet" bath only. Acrylic fiber, rayon fiber are
manufactured through wet spinning.
Dry Spinning: It is also used for polymers that have to be dissolved in a solvent.
However, solidification results from evaporation of the solvent. After dissolving the
polymer in a volatile solvent, the solution is pumped through a spinneret. As the fibres
emerge from the spinneret, air or inert gas is used to evaporate the solvent which
results in solidification of the fibers that can be collected on a take-up wheel. The
fibers are stretched which provides for orientation of the polymer chains along the
fiber axis. This technique is used only for polymers which cannot be melt spun
because of the safety and environmental concerns concerned with solvent handling.
Dry spinning may be used for manufacturing acetate fiber, triacetate fiber, acrylic
fiber.
Melt Spinning: is used for the polymeric fibers or the polymers that can be melted. The polymer is
melted and then pumped through a spinneret. The cooled and solidified molten fibers get collected on a
take-up wheel. The fibers, when stretched in both, the molten and solid states, facilitate orientation of
the polymer chains along the fiber axis. Melt spun fibers can be forced through the spinneret in different
cross-sectional shapes such as round, trilobal, pentagonal, octagonal among others. Trilobal-shaped
fibers are capable of reflecting more light which give a sparkle to the fabrics. Pentagonal-shaped and
hollow fibers are soil and dirt resistant and as such are used for making carpets and rugs. Octagonal-
shaped fibers offer glitter-free effects whereas hollow fibers trap air, creating insulation. Polymers like
polyethylene terephthalate and nylon 6,6 are melt spun in high volumes. Nylon fiber, olefin fiber,
polyester fiber, saran fiber, etc. are also manufactured through melt spinning.

Gel spinning: It is also known as dry-wet spinning because the filaments first pass through air and then are cooled
further in a liquid bath. Gel spinning is used to make very strong and other fibers having special characteristics. The
polymer here is partially liquid or in a "gel" state, which keeps the polymer chains somewhat bound together at various
points in liquid crystal form.

This bond further results into strong inter-chain forces in the fiber increasing its tensile strength. The polymer chains
within the fibers also have a large degree of orientation, which increases its strength. The filaments come out with an
unusual high degree of orientation relative to each other, further enhancing strength. The high strength polyethylene
fiber and aramid fibers are manufactured through this process.

Whatever spinning process is applied, the fibers are finally drawn to increase strength and orientation. This may be done
while the polymer is still in the process of solidifying or after it has completely cooled down. Drawing pulls the
molecular chains together and orients them along the fiber axis, resulting in a considerably stronger yarn.
Acrylic fiber:
Most of the organic contains a major amount of acrylonitrile, the other monomers such as methacrylate, vinyl acetate,
vinyl chloride and acrylamide are present upto 15% only. Solution spinning only is used for acrylonitrile because of the
heat sensitive nature. dimethyl formamide is used as solvent for wet spinning .
Acrylic fiber is manufactured by copolymerizing acrylonitrile with vinylchloride. Acrylonitrile, comonomer and catalyst
are charged into an autoclave (1). The polymerisation is carried out in presence of acid catalyst such as amonium
persulphate in aqueous medium at low temperature. The polymer mass after discharging is mixed with inhibitors in
reactor (2). The mass is then washed with water to remove the unreacted monomers. The polymer mass is then dried by
hot air. The polymer powder is packed and transferred to wet spinning section. All these polymers posses soft touch,
resistance to creasing and quick drying. They look like wools, and replace wool. Though these fibers exhibit high
hydrophobic nature, the new fiber developed by Bayer A.G can absorb as high as 30% moisture, matching the properties
of wool.
Viscose Rayon
A river of spruce logs floating downstream to the mills
where they are debarked, chipped into small pieces and boiled in these digesters with sodium
bisulphite. The boiled pulp is then washed, shredded and made into sheets of pure wood pulp.
Here the sheets of wood pulp have been transported to the viscose manufacturer
where they are being weighed prior to steeping in the required amount of caustic soda
solution
After steeping for the required period, the sheets are squeezed to remove excess caustic soda
before being kneaded into 'alkali cellulose crumbs' in a pfleiderer such as that shown here. The
crumbs are then emptied out and left to mature for a short period
The crumbs are then churned with the correct amount of carbon disulphide, in what is a
scaled-up version of the butter churn used by The Viscose Spinning Syndicate. The
cellulose is converted into cellulose xanthate (viscose) during this process
The viscose is aged and stored in tanks from whence it is forced by air pressure to the a large
array of spinning machines.
Each spinning machine has a spinnerette containing many holes, each producing a
strand. (enlarged view)
A gear pump (lower part of picture) controls the flow of viscose through the candle filter
(top of picture) which removes any particles which might block the spinnerette (left of
picture) The viscose is forced through the spinnerette into an aqueous solution where it
is converted back to cellulose in the form of continuous filaments. The strand of
filaments is collected on the rim of a wheel (godet) turning at a constant speed. The
filaments are then stretched whilst still wet by passing over a second godet rotating at a
faster rate.
VISCOSE RAYON

The process of manufacturing viscose rayon consists of the following steps mentioned, in the order that they are
carried out: (1) Steeping, (2) Pressing, (3) Shredding, (4) Aging, (5) Xanthation, (6) Dissolving, (7)Ripening, (8)
Filtering, (9) Degassing, (10) Spinning, (11) Drawing, (12)Washing, (13) Cutting. The various steps involved in the
process of manufacturing viscose are illustrated and clarified below.

Steeping: Cellulose pulp is immersed in 17-20% aqueous sodium hydroxide (NaOH) at a temperature in the range of
18 to 25° C in order to swell the cellulose fibers and to convert cellulose to alkali cellulose.

(C6H10O5)n + nNaOH ---> (C6H9O4ONa)n + nH2O

Pressing: The swollen alkali cellulose mass is pressed to a wet weight equivalent of 2.5 to 3.0 times the original pulp
weight to obtain an accurate ratio of alkali to cellulose.

Shredding: The pressed alkali cellulose is shredded mechanically to yield finely divided, fluffy particles called
"crumbs". This step provides increased surface area of the alkali cellulose, thereby increasing its ability to react in the
steps that follow.

Aging: The alkali cellulose is aged under controlled conditions of time and temperature (between 18 and 30° C) in
order to depolymerize the cellulose to the desired degree of polymerization. In this step the average molecular weight
of the original pulp is reduced by a factor of two to three. Reduction of the cellulose is done to get a viscose solution of
right viscosity and cellulose concentration.
Xanthation: In this step the aged alkali cellulose crumbs are placed in vats and are allowed to react with carbon
disulphide under controlled temperature (20 to 30° C) to form cellulose xanthate.

(C6H9O4ONa)n + nCS2 ----> (C6H9O4O-SC-SNa)n

Side reactions that occur along with the conversion of alkali cellulose to cellulose xanthate are responsible for the
orange color of the xanthate crumb and also the resulting viscose solution. The orange cellulose xanthate crumb is
dissolved in dilute sodium hydroxide at 15 to 20° C under high-shear mixing conditions to obtain a viscous orange
colored solution called "viscose", which is the basis for the manufacturing process. The viscose solution is then
filtered (to get out the insoluble fiber material) and is deaerated.

Dissolving: The yellow crumb is dissolved in aqueous caustic solution. The large xanthate substituents on the
cellulose force the chains apart, reducing the inter-chain hydrogen bonds and allowing water molecules to solvate and
separate the chains, leading to solution of the otherwise insoluble cellulose. Because of the blocks of un-xanthated
cellulose in the crystalline regions, the yellow crumb is not completely soluble at this stage. Because the cellulose
xanthate solution (or more accurately, suspension) has a very high viscosity, it has been termed "viscose".

Ripening: The viscose is allowed to stand for a period of time to "ripen". Two important process occur during
ripening: Redistribution and loss of xanthate groups. The reversible xanthation reaction allows some of the xanthate
groups to revert to cellulosic hydroxyls and free CS2. This free CS2 can then escape or react with other hydroxyl on
other portions of the cellulose chain. In this way, the ordered, or crystalline, regions are gradually broken down and
more complete solution is achieved. The CS2 that is lost reduces the solubility of the cellulose and facilitates
regeneration of the cellulose after it is formed into a filament.

(C6H9O4O-SC-SNa)n + nH2O → (C6H10O5)n + nCS2 + nNaOH

Filtering: The viscose is filtered to remove undissolved materials that might disrupt the spinning process or cause
defects in the rayon filament.
Degassing: Bubbles of air entrapped in the viscose must be removed prior to extrusion or they would cause voids, or
weak spots, in the fine rayon filaments.

Spinning - (Wet Spinning): Production of Viscose Rayon Filament: The viscose solution is metered through a
spinnerette into a spin bath containing sulphuric acid (necessary to acidify the sodium cellulose xanthate), sodium
sulphate (necessary to impart a high salt content to the bath which is useful in rapid coagulation of viscose), and zinc
sulphate (exchange with sodium xanthate to form zinc xanthate, to cross-link the cellulose molecules). Once the
cellulose xanthate is neutralized and acidified, rapid coagulation of the rayon filaments occurs which is followed by
simultaneous stretching and decomposition of cellulose xanthate to regenerated cellulose. Stretching and
decomposition are vital for getting the desired tenacity and other properties of rayon. Slow regeneration of cellulose
and stretching of rayon will lead to greater areas of crystallinity within the fiber, as is done with high-tenacity rayons.

The dilute sulphuric acid decomposes the xanthate and regenerates cellulose by the process of wet spinning. The outer
portion of the xanthate is decomposed in the acid bath, forming a cellulose skin on the fiber. Sodium and zinc
sulphates control the rate of decomposition (of cellulose xanthate to cellulose) and fiber formation.

(C6H9O4O-SC-SNa)n + (n/2)H2SO4 --> (C6H10O5)n + nCS2 + (n/2)Na2SO4

Drawing: The rayon filaments are stretched while the cellulose chains are still relatively mobile. This causes the
chains to stretch out and orient along the fiber axis. As the chains become more parallel, interchain hydrogen bonds
form, giving the filaments the properties necessary for use as textile fibers.

Washing: The freshly regenerated rayon contains many salts and other water soluble impurities which need to be
removed. Several different washing techniques may be used.
Cutting: If the rayon is to be used as staple (i.e., discreet lengths of fiber), the group of filaments (termed "tow") is
passed through a rotary cutter to provide a fiber which can be processed in much the same way as cotton.
Natural rubber
Natural rubber is an elastomer (an elastic hydrocarbon polymer) that was originally derived from latex,
a milky colloid found in the sap of some plants. The plants would be „tapped‟, that is, an incision made
into the bark of the tree and the latex sap collected and refined into a usable rubber. The purified form of
natural rubber is the chemical polyisoprene, which can also be produced synthetically. Natural rubber is
used extensively in many applications and products, as is synthetic rubber.

The commercial source of natural rubber latex is the para rubber tree (Hevea brasiliensis).

Chemical makeup
Latex is a natural polymer of isoprene (most often cis-1,4-polyisoprene) – with a molecular weight of
100,000 to 1,000,000. Typically, a small percentage (up to 5% of dry mass) of other materials, such as
proteins, fatty acids,resins and inorganic materials (salts) are found in natural rubber. Polyisoprene is also
created synthetically, producing what is sometimes referred to as "synthetic natural rubber".

Some natural rubber sources called gutta-percha are composed of trans-1,4-polyisoprene, a structural
isomer which has similar, but not identical, properties.

Natural rubber is an elastomer and a thermoplastic. However, it should be noted that as the rubber is
vulcanized, it will turn into a thermoset. Most rubber in everyday use is vulcanized to a point where it
shares properties of both; i.e., if it is heated and cooled, it is degraded but not destroyed.

Vulcanization of rubber creates more disulfide bonds between chains, so it shortens each free section of
chain. The result is that the chains tighten more quickly for a given length of strain, thereby increasing the
elastic force constant and making rubber harder and less extensible.

Carbon black is often used as an additive to rubber to improve its strength, especially in vehicle tires.
Synthetic rubber is any type of artificial elastomer, invariably a polymer. An elastomer is a material
with the mechanical (or material) property that it can undergo much more elastic deformation under
stress than most materials and still return to its previous size without permanent deformation. Synthetic
rubber serves as a substitute for natural rubber in many cases, especially when improved material
properties are required. Nowadays synthetic rubber is used a great deal in printing textile. In this case it
is called rubber paste. In most cases titanium dioxide is used with copolymerization and volatile matter
in producing such synthetic rubber for textile use. Moreover this kind of preparation can be considered
to be the pigment preparation based on titanium dioxide.

Comparison of natural and synthetic rubber

Natural rubber coming from latex is mostly polymerized isoprene with a small percentage of impurities
in it. This limits the range of properties available to it. Also, there are limitations on the proportions of
cis and trans double bonds resulting from methods of polymerizing natural latex. This also limits the
range of properties available to natural rubber, although addition of sulfur and vulcanization are used to
improve the properties.

Synthetic rubber can be made from the polymerization of a variety of monomers including isoprene (2-
methyl-1,3-butadiene), 1,3-butadiene, chloroprene (2-chloro-1,3-butadiene), and isobutylene
(methylpropene) with a small percentage of isoprene for cross-linking. These and other monomers can
be mixed in various desirable proportions to be copolymerized for a wide range of physical, mechanical,
and chemical properties. The monomers can be produced pure and the addition of impurities or additives
can be controlled by design to give optimal properties. Polymerization of pure monomers can be better
controlled to give a desired proportion of cis and trans double bonds.
Polybutadiene

Polybutadiene is a synthetic rubber that is a polymer formed from the polymerization of the monomer 1,3-
butadiene. It has a high resistance to wear and is used especially in the manufacture of tires. It has also
been used to coat or encapsulate electronic assemblies, offering extremely high electrical resistivity.

Polymerization of butadiene

1,3-Butadiene is an organic compound which is a rather simple conjugated diene hydrocarbon;

Polybutadiene can be formed from many 1,3-butadiene monomers undergoing free radical polymerization
to make a much longer polymer chain molecule.
Properties
Polybutadiene is a highly resilient synthetic rubber. Due to its outstanding resilience, it can be used for the
manufacturing of golf balls. Heat buildup will be less in polybutadiene rubber based on vulcanization
subjected to repeated flexing during service. This property leads to its use in the sidewall of truck tires.
Good abrasion resistance of this rubber also leads to its use in the tread portion of truck tires; however,
skidding may be a problem in passenger car tires due to low rolling resistance. For high temperature
curing, polybutadiene may be blended with natural rubber and other rubbers, due to resistance in reversion
of physical properties. Polybutadiene rubber can be used in water seals for dams due to its low water
absorption properties. Rubber bullets and road binders can be also produced by polybutadiene rubber.

Copolymers
1,3-butadiene is normally copolymerized with other types of monomers such as styrene and acrylonitrile to
form rubbers or plastics with various qualities. The most common form is styrene-butadiene copolymer,
which is a commodity material for car tires. It is also used in block copolymers and tough thermoplastics
such as ABS plastic. This way a copolymer material can be made with good stiffness, hardness, and
toughness. Because the chains have a double bond in each and every repeat unit, the material is sensitive to
ozone cracking.

Processing
Polybutadiene rubber is seldom used alone, but is instead mixed with other rubbers. Polybutadiene is
difficult to band in a two roll mixing mill. Instead, a thin sheet of polybutadiene may be prepared and kept
separate. Then, after proper mastication of natural rubber, the polybutadiene rubber may be added to the
two roll mixing mill. A similar practice may be adopted, for example, if polybutadiene is to be mixed with
styrene-butadiene.
In an internal mixer, natural rubber and/or styrene-butadiene may be placed first, followed by
polybutadiene.
Uses

•Polybutadiene is largely used in various parts of automobile tires. Its use in the tread portion of giant
truck tires helps to improve the abrasion, i.e. less wearing, and to run the tire comparatively cool, since
the internal heat comes out quickly.

•In the sidewall of truck tires, the use of polybutadiene rubber helps to improve fatigue to failure life due
to the continuous flexing during run. As a result, tires will not blow out in extreme service conditions.

•Polybutadiene rubber may be used in the inner tube of hoses for sandblasting, along with natural rubber.
The main idea is to increase resilience. This rubber can also be used in the cover of hoses, mainly
pneumatic and water hoses.

•This rubber can also be used in railway pads, bridge blocks, golf balls, etc.

•In car tires, polybutadiene rubber can be used with SBR in the tread portion.

•Polybutadiene has high resilience properties. 100% Polybutadiene Rubber based vulcunizate is used as
crazy balls i.e. a ball if you drop from 6th floor of a house it will rebound up to 5½ to 6th floor
considering no air resistance.

•Polybutadiene Rubber is blended with Polystyrene to prepare High Impact Polystyrene (HIPS).
Styrene-Butadiene or Styrene-Butadiene-Rubber (SBR) is a synthetic rubber copolymer consisting of
styrene and butadiene. It has good abrasion resistance and good aging stability when protected by
additives, and is widely used in car tires, where it is blended with natural rubber.

SBR can be produced from solution or as emulsion. In both instances, the reaction is via free radical
polymerization. Pressure reaction vessels are required and usually charged with the two monomers, a free
radical acid and a chain transfer agent such as an alkyl mercaptan. The latter prevents high molecular
weight and high viscosity product from forming. High styrene-content rubbers are hard.

Major application characteristics: good physical properties; excellent abrasion resistance; but sensitive to
oil, wastewater and ozone; electrical properties good, but not outstanding.

Applications
The elastomer is used widely in pneumatic tires, shoe heels and soles, gaskets and even chewing gum. It
is a commodity material which competes with natural rubber. Latex (emulsion) SBR is extensively used
in coated papers, being one of the most cost-effective resins to bind pigmented coatings. It is also used in
building applications, as a sealing and binding agent behind renders as an alternative to PVA, but is more
expensive. In the latter application, it offers better durability, reduced shrinkage and increased flexibility,
as well as being resistant to emulsification in damp conditions.
Cross-Linking

In addition to the bonds which hold monomers together in a polymer chain, many polymers
form bonds between neighboring chains. These bonds can be formed directly between the
neighboring chains, or two chains may bond to a third common molecule. Though not as
strong or rigid as the bonds within the chain, these cross-links have an important effect on
the polymer. Polymers with a high enough degree of cross-linking have "memory." When
the polymer is stretched, the cross-links prevent the individual chains from sliding past each
other. The chains may straighten out, but once the stress is removed they return to their
original position and the object returns to its original shape.

One example of cross-linking is vulcanization . In vulcanization, a series of cross-links are

introduced into an elastomer to give it strength. This technique is commonly used to
strengthen rubber.