UNIT-1

POLYMER TECHNOLOGY

Introduction :

Polymer plays a major role in our daily life .Most of the articles we use are either completely or partially
made up of polymers. polymers are widely used in domestic ,industrial and medicinal fields. Man termed
the later part of twentienth century as the plastic age

We find use for plastics in all our activities of daily life starting with brushes ,combs, mugs, buckets, ball
point pens, carry bags, rain coats, clothes made up of synthetic materials like polyesters----are all
polymers.

Nature has also given us a number of polymers like proteins, rubber, DNA, RNA etc….

The term “polymers” was coined by “Jones Jacob Berzilius”.The word polymer is derived from Greek
word poly meaning “many” and meros meaning “Unit”.

Definition :

Polymers are large molecules (macro molecules) constituted by repeating structural units (monomers)
which are connected by covalent chemical bonds

Degree of Polymerisation :

It is usually defined as the number of monomeric units or repeating units (n) in a polymer
Total molecular weight of the polymer ( Mn )
DP=
Molecular weight of monomeric unit ( Mo )

Ex :Nylon 6,6 .The repeating unit contains the two monomeric units –NH(CH2)6NH- and – -(CH2)4-
,so that a chain of 1000 monomeric uits corresponds to 500 repeating units.

Functionality:

In polymerization, the monomers are linked to each other throughcovalent bonds. So the monomer should
have two bonding sites or reactive sites .The number of active bonding sites of a monomer is referred to
as its functionality

Ex ; Ethylene has two reactive or bonding sites i.e; there are two new single bonds formed when the
ethylene double bond is broken

1) nCH2=CH2---- -(-CH2-CH2-)n

Ethylene Bi functional monomer

Monomer with 3 functional sites is called as tri functional monomer

Monomer with 4 functional sites is called as tetra functional monomer

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Regarding poly functional groups, monomer units are connected to each other by covalent bonds resulting
in the formation of three dimensional network
Ex ;Bakelite, Urea formaldehyde resin

TYPES OF POLYMERISATION

Polymerisation

The process of formation of large molecule by repeated combination of many small and simple
molecules.

The polymerisation can be achieved by Three methods.

A) Addition B) Condensation

(a) Addition or chain growth polymerization

Addition polymerization involves the self addition of n-

saturated molecule to form a large molecule without elimination of any by product by rapid chain
reaction.

B) Condensation or step wise or step growth polymerization :

Polycondensation is brought about by monomers containing 2or more reactive functional groups (OH,
CO, NH2) condensing with each other . The condensation polymerization proceeds by a stepwise inter
molecular condensation of monomers into a polymer with the elimination of smaller molecules called by
product like water alcohol, ammonia etc.

Ex 1) nylon 6 6

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2)TERYLENE OR DACRON

(C) Co-polymerisaton

Copolymerization is the addition polymerization in which a large molecule is formed by the

repeated combination of two or more types of monomers.

Ex: n CH2=CH-CH=CH2 + n C6H5-CH=CH2 --- [CH2-CH=CH-CH2-CH(C6H5)-CH2]n

Butadiene Styrene Polystyrene or co styrene

Stereo specific polymers-:

Tacticity-: The orientation of monomeric units on functional groups in a polymer can takes place in order
or disorder manner with respect to main chain

Precise knowledge of tacticity of a polymer helps to understand at what temperature the polymer melts,
how soluble in a solvent, its mechanical properties, physical properties like crystallinity, rigidity of the
polymer.

Based on the stereo chemical orientation of atoms or groups at asymmetric carbons, the polymers can be
classified as

1) Atactic polymer-:
In these polymers, the substituents are placed randomly along the chain .

Ex-;pvc ,poly styrene

Due to their random nature, the polymers are amorphous ,low melting point

mechanically weak.

2) Syndiotactic polymers:

In these polymers, substituents are arranged in alternative position

Ex-: Gutta percha (natural rubber)

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 These polymers , have high crystallinity and high melting point

3) Isotactic polymers -:

In these polymers , substituents are present on the same side of the polymer chain
Ex :polypropylene

These polymers , have high crystallinity and high melting point

Properties of polymers :

The monomeric units are generally micro in structure and the mode of their linking leads to the formation
of macro molecules(polymer).the overall structure is given by the number and chemical nature of
monomeric units

Polymer has two type of bonds

A)Chemical or Covalent bonds through which them atoms in the polymer are strongly connected to each
other by about 1.5A.

B) Weak inter molecular forces through which the polymer chain are weakly holkd to each other about 3-
4A.

So these two are played a vital role in structure and properties of polymer

1)Physical properties : Physical properties of polymers:

CRYSTALLINITY

Crystallite is defined as a small region of a macro molecular material in which portions of a large
molecules linked to each other in some regular way.The degree of orderly arrangement is called
Crystallinity

The irregularly coiled and tangled parts of the polymer is called amorphous region.

Any polymer contains 80% crystalline and 20% amorphous portions.

MOLECULAR WIEGHT

During the polymerization process the growing polymer chain may terminate at different lengths,as a
result the polymer molecule s have different molecular weights .Hence the molecular polymer weight of
the polymer is expressed as Average molecular weight.

Broadly Average molecular weights are 2 types:

1)Number average molecular weight 2)weight average molecular weight.

1) Number average molecular weight :

It depends upon the number of monomer units present in the polymer.it is determined by dissolving the
polymer in a solvent and colligative properties of the solution are measured.

2)weight average molecular weight.

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 It depends upon the weightof monomer units present in the polymer.it is determined by dissolving the
polymer in a solvent and colliodal properties of the solution are measured.

SOLUBILITY:

Polymers when dissolved in a suitable solvent absorbs the solvent and swells in size,slowly it
goes into the solvent forming a heterogenous solution.

EFFECT OF TEMPERATURE room temperature all the polymers exists as solid s in rubbery visco
elastic state.when the temperature is futher raises to boiling (Tb),the polymer breaks into individual units
(monomers).hence the polymers have solid and liquid phases but not gaseous phase.

When it is cooled below zero ,polymer acts as glass .it becomes hard ,brittle and transparent.

The temperature below which it acts as a glass is known as glassy transistion temperature.

2)Mechanical properties :

a)Strength :The magnitude of chemical bonds forces between the atoms and Distribution of the attraction
forces between the polymer molecules mainly effects the properties of polymer.The strength of inter
molecular forces can be increased by either increasing the chain length or increasing the presence of
groups like –oH, -COOH,-COOR.Strength also depends on the shape of the molecules.if the shape of
Polymer is simple and uniform, the polymer molecule has less strength

Ex ; In PVC,large size of chlorine atoms are present on alternative carbon atoms in the polymer.The large
size of chlorine atoms

ii)Elastic character ;

In normal state, polymer is amorphous due to random arrangement Of snarls.(SNARLS: ELASTOMERS

ARE ONLY SLIGHTLY CROSS- LINKED, AMORPHOUS AND RUBBR LIKE POLYMERS
WITH LONG CHAIN AND FR ROTATIONG groups.in the absence of Deforming forces,the
polymer chain has peculiar configuration of irregulariy coiled and entangled snarlWhen the
polymers are stretchd ,the cross linked begin to disentangle and straighten out,Such orientation of
chain causes hardness,stiffness,crystallinity of material due ti increase of the attraction forces
between thg chains.

iii)Toughness:

The impact strength is measured as toughness .Below glass transistion temperature(Tg) the polymer
breaks with abrittle fracture and they become tougher wen the temperature proceeds from room
temperature to Tg.The size of the crystalline structure also determines the toughness .The small
spherical crystalline masses increase toughness.

PLASTICS

DEFINITION: plastics are large chain polymeric molecules that have ability to mould into desired shape
under the heat and pressure.

TYPES OF PLASTICS

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THERMOPLASTICS; the polymers which become soft on heating and hard on cooling t he plastics
which can be reshaped and recycled.

Ex :polyvinyl chloride, polyethylene

THERMOSETTING: the plastics hard and rigid on heating. they cannot be recycled or reshaped.

Ex: Bakelite, polyesters

FABRICATION METHODS

COMPRESSION MOULDING

Compression moulding is the most common process used with thermosetting materials and is usually not
used for thermoplastics. With this process , the material is squeezed into its desired shape with the help
of pressure and heat Plastic moulding power and other material are added to the mix in order to create
special qualities or to strength the final product . when the mould is closed and heated, the material goes
through a chemical change that causes it to harden into its desired shape . The temperature amount of
pressure, and length of time utilized during the process depends on the desired outcome. In the figure
compression moulding for thermoplastics is shown.

Advantages

 Relatively low capital and low tooling cost

 Low mold maintenance
 Retains Mechanical and electrical properties

Disadvantages:

 It is not economical for making a small no. of parts

 There is a limitation on molding depth

Applications:

 This method is used to prepare shades, crockery items, electrical switches, toys etc.

2 INJECTION MOULDING

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The main method used for processing plastic is injection moulding. With this process, the plastic is placed
into a hopper . the hopper then feeds the plastic into a heated injection unit, where it is pushed through a
long chamber with a reciprocating screw. Here it is softened to a fluid state.

A nozzle is located at the end of the chamber . the fluid plastic is forced through the nozzle into A cold
closed mould. The halves of the mould are held shut with a system of clamps. When the plastic is
cooled and solidified the halves open and the finished product are ejected from the press. Themosetting
materials ususlly are not processed with injection moulding because they will soften; they harden to an
infusible state. If they are processed with injection moulding , they need to be moved through the
heating chamber quickly so they do not set.

Advantages:

 Fast Production, Low labour cost

 Design Flexibility, Good colour control
 Can be Used to produce very small parts

Disadvantages:

 Injection molding machine cost is high

 Molds are also costly. However this method is widely used for the preparation of complex
materials

Applications:

 This Method is used to prepare chairs ,Safety Helmets, Mobile parts, Fan in CPU etc.

EXTRUSION MOULDING

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It is mainly used in moulding of thermoplastics into articles of uniform cross section like tubes
,rods,sheets,wires cables etc the thermoplastic ingredients are heated to a plastic state and then pushed by
means of a screw conveyor into a die ,having the desired shape inside .it is then cooled and the solid
articles will be ejected out.

Advantages:

 It is most efficient and rapid method for producing long and continuous articles
 It has a low cost relative to other molding process
 It provides considerable flexibility in manufacturing products

Disadvantages:

 It can be applicable only for linear polymers

 When the hot plastic exits the extruder, it frequently expands

Applications:

 This method is used to prepare Long continuous tubes, tooth paste tubes, Wires, straws etc.

BLOWING MOULDING

It is used in fabricating hallow articles like drink bottles containers etc., it is used in fabricating
thermoplastics.a hot softened thermo plastic tube called parison is placed inside a two piece hallow
mould. The halves of the mould are closed and parison is now blown with compressed air. The parison is

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inflated by the air and expands in the shape of the mould inside. The mould is allowed to cool and the
article is ejected out on opening.

Advantages:

 Can be prepare large Hallow parts with thin walls

 Low tooling cost, fast Production rate
 Recyclable

Disadvantages:

 Thick walls cannot be prepared by this method

 This method is Only for hallow parts

Applications:

 This method is used to prepare Fuel tanks, Water tanks, Water bottles, soft drink bottles, Recycle
bins etc.

COMPOUNDING OF PLASTICS

This is the process in which chemicals are added to the polymers in order to acquire desired qualities in
the plastic. Compounding of plastics increases tensile strength and mechanical strength of the polymers
and induces plasticity to the polymers.

Different compounding agents are as follows:

1) Binder:
it is a material which holds all other compounding agent like colourants plasticizers, stabilizers
etc., It is nothing but the polymer used such as poly ethylene, polystyrene vinyl chloride etc. the
polymers used are known as resins. Resins can be thermo plastics are thermo settings.
2) Filler: Cheap inorganic material reduces cost ,improves physical properties

Particulate filler: It lowers cost and increases hardness and tensile strength

Eg : asbestos clay,silica, mica.

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 Fibrous fillers: increase tensile strength ,impact and wear and tear resistance

Eg :scraps of cloths and nylon.

3) Plasticizers: They induce plasticity and flexibility .it reduces Tg.

Eg: triphenyl phosphate, fatty acid esters .

3)Stabilizers: It is also called as anti oxidants.It prevents photo chemical and thermal degradation .

eg: alkyl phenols ,naphthnols.

4)Colourants : They provide colour to the plastic

Eg :carbon black- black,

Titanium oxide –white
Lead chromate-yellow
Iron oxide-red

5) Accelerators (catalysts)

They accelerate polymerization.eg : H2O2,ZnO,NH3

INDIVIDUAL POLYMERS

(1) Poly vinyl chloride(pvc)

It is a thermoplastic polymer which is obtained through Addition polymerization in which the monomer
is vinyl chloride.

The method generally used are suspension, Micro suspension and emulsion polymerisation .Most widely
used is suspesnsion , in which there is uniform particle size of PVC resin.

Preparation;

PVC is prepared by free radical Addition polymerisation process.

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Vinyl chloride and water are introduced into polymerisation reaction with polymerisation under pressure
.The PVC slurry is degassed and stripped to remove excess monomer and water through centrifugation.
The slurry is then dried further into hot air bed. Then the powder is sieved before storage .

Properties

(1)PVC is colourless ,odour less and non-inflammable substance.

(2)It has excellent resistance to oil as well as weathering .

(3)It is resistant to atmospheric conditions like O2,CO2 and moisture.

(4)It is insoluble in alcohol, water and hydrocarbons

(5)The softening point of PVC is 1480C

Applications

It is used in making building materials like drainage pipes and window frames.

It is used to make consumable liquid bottles for oils ,mineral water etc.

it can also be used in making plastic rain wear ,radio components .

it is used in making refrigerator components

BAKELITE

It is prepared by Dr.Leo Bakeland

It is a thermosetting plastic. The preparation involves condensation polymerization

PREPARATION:

It is a polymer formed from phenol and formaldehyde in the presence of an acid.

It follows three steps 1)formation of methylol derivative based on P/F ratio

2)formation of Novalac from methylol derivative

3)Combination of Novalac

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Properties of Bakelite

It is hard rigid and strong .

Resistant to water ,oils .acids and all most all solvents .

It is a thermosetting polymer and cross linked polymer.

It is resistant to abrasion and stratches .

It is an insulator.

Applications of Bakelite:

It is used in making electrical insulator parts such as switches and switch boards .

It is used in making moulded articles like telephone parts .

It is used as ion exchanger in the water purification process .

It is used in paints.

Used as an adhesive in grinding wheels

RUBBERS AND ELASTOMERS

 Rubbers are polymers which are the property of elasticity. hence rubbers can be called
elastomers.

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  Rubbers are chemically “poly isoprene “molecules. Which 2-methyl-1,3-butadiene.
 Rubbers and different kinds of it are produced from latex obtained from rubber treessuch as
Hevea brasiliensis, Palagum gutta and Dischopsis gutta.rubbers have the property of resilience “a
polymer expands on application of stress on its end to twice or more and regains its original
length on releasing the force ” .
 The property of elasticity to rubbers is due to its coiled structure called Snarls and the
vanderwaals forces existing between the polymer chains .

HIGHLY COILED SNARLS DECOILED RUBBER

DRAWBACKS OF RAW RUBBER

Vulcanization transforms the rubber that is weak, thermoplastic mass of no use into a strong elastic and
tough rubber

 Less tensile strength

 Provides poor resilience
 Shows no resistance to organic solvents such as benzene ccl4 etc:
 Absorb water absorption
 Working temperature range is -10 to 60C
 elasticity is less

COMPOUNDING OF RUBBER

The process of mixing of different additives to the rubber to improve its properities is called
compounding of rubber

1)vulcanizing agents ; H2S,S2Cl2

VULCUNISATION OF RUBBER.

The process of addition of sulphur to rubber at a temperature of 140 to 180 is called as vulcanization.

It improves the undesireable properties of the rubber to usefull ones by forming three dimensional cross
linking between the polymer chains.bonded to each other by sulphur atoms .

It brings about stiffening of the polymer

POLY ISOPRENE VULCUNISED RUBBER

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ADVANTAGES OF VULCUNISATION

 Vulcanization transforms the rubber that is weak, thermoplastic mass of no use into a strong
elastic and tough rubber.
 Increases tensile strength
 Provides resilience
 Shows resistance to organic solvents such as benzene ccl4 etc:
 Greatly reduces water absorption .
 Reduces the reactivity with O2,O3.
 Working temperature range is -40 to 100.
 tensile strength increases by 10 times than normal rubber(from 200 to 2000Kg /cm2).
 elasticity is gretly reduced .

2)Along with sulphur some other additives are often used such as

 Accelerators: speeds up the reaction

Ex; Zno; magnesia
 Antioxidants: reduces the deterioration process
Ex: phenyl napthyl amines,phosphites
 Rienforcing agents : Provides strength to rubber
Ex –BaSO4,MgCO3,
 Inert fillers :alters the physical properties.
Ex :clay,silica
 Plastisicer:soften the polymer
.ex-veg oils ,waxes,
 Colourants: Imparts colour to rubber
Ex:TiO2 - white
Carbon black - black
Ferric oxide - red

SYNTHETIC RUBBERS :

 Synthetic rubber is artificially made polymer material which acts as an elastomer.

 They act as substitute for natural rubber in many cases especially when improved materials
properties are required

STYRENE- BUTADIENE RUBBER:SBR OR BUNA-S OR GRS OR AMPERICOL

It is a copolymer consisting of styrene and butadiene and it is an addition product

PREPARATION

It is prepared by free radical polymerization of the two monomers in the ratio 75%butadiene and 25%
styrene. And catalyst used is sodium

STYRENE BUTADIENE STYRENE BUTADIENE RUBBER

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PROPERTIES

 Excellent resistance to high load bearing capacity

 Sensitive to oil waste water and ozone
 Electrical properties are good but not outstanding
 Poorer resilience than that of natural rubber which restricts its use in tire industry.

APPLICATIONS:

 it is widely used in pneumatic tyres.

 shoe heels and soles ,gaskets and even chewing gums
 extensively used in coated papers being one of the most effective resin to bind pigmented
coatings
 used for electrical insulation

POLYSULPHIDE RUBBER : OR THIOKOL OR GRP

It is the condensation product of ethylene di halide and alkali sulphide

It is a linear polymer

DIHALIDE ALKALI SUlPHIDE THIOKOL RUBBER

PROPERTIES

 The properties of the material depends upon the length of the aliphatic groups and the number of
sulphur atoms present in it
 The product is rubbery the monomer has 4 sulphur atoms
 The monomer with 2 sulphur atoms do not behave as elastomer.
 It is resistant to swelling .
 It is resistant to oils and solvents , fueloils lubricating oils gasoline and kerosene Have no effect
on Thiokol.
 Thiokol films are impermeable to gases to a large extent
 It cannot be vulcanized

APPLICATIONS

 Used to make sealants, gaskets , ballons,fabric coatings

 Due to low permeability it is used to make gasoline hoses
 Liquid Thiokol can be cured at room temperature to tough solvent resistant rubbers
 These liquid compounds can be used as gasoline tank linings and sealants , liners for aircraft
components and in variety of sealing applications
 The liquid polymers when combined with oxidizers ,it burn with great intensity and generate
large volume of gas . thus it can be used in solid –fuel rocket propellent.

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