Chapter 7

High Polymer
 Basic Definitions
Polymer
-Is a large molecule built by the repetition of small , simple
chemical unit called monomer.
-Covalently –linked
-103 to 107

Monomer
-simple molecule with two or more binding sites through
which it forms covalent linkage with other monomer
molecules to form the macromolecules.
e.g alkenes, vinyl chloride, adipic acid ( two bonding sites)
NH3, H2O , CH3CH2OH are not monomers
Polymerization
-The chemical reaction in which a monomer is converted to the
polymer under specific conditions.
-Monomer initiator required Polymer

vinyl chloride peroxide PVC Cl

n[ CH2=CH –Cl ] [ CH2 - CH ]n

Functionality
No. of bonding sites present in a molecule of the monomer.

CH2 =CH2 (ethene) bonding sites =2 functionality = 2 bifunctional

CH3-CH =CH2 (propene), CH2 = CHCl (vinyl chloride),

OH - OH

CH2 - CH2 Diamine, [H 2N-(CH2)6 –NH2] hexamethylene-

Degree of polymerization(DP)
The no. of repeating units present in a polymer molecule.

n[ CH2= CH2] [CH2 - CH2 ]n

n = a whole number , the degree of polymerization

Molar mass of = degree of x molar mass

addition polymer polymerization of monomer

Mn = DP x molar mass of monomer

Polymer do not have the same DP and show variation in molar mass.
# only average DP and average molar mass (Mn) #
Molar masses of polymers
(i) Number average molar mass Mn
(ii) Weight average molar mass Mw

(i) Number average molar mass Mn

n 1 M1 + n2M2 + …….. + niMi niMi

Mn = =
n1 + n2 + ………… + ni ni

n1 = molecules have molar mass M1 n2 = molecules have molar mass M2

Mn is the ratio of the sum of molar masses of individual molecules to

the total number of molecules in the mixture.
 Weight average molar mass Mw

w1M1 + w2M2 + …….. + wiMi wiMi

Mw = =
w1 + w2 + ………… + wi wi
w1 = the mass of polymers with molar mass M1
w
Numbers of moles n= , w =nM
M
n1M21 + n2M22 + …….. + niM2i niM2i
Mw = =
n1M1 + n2M2 + ………… + niMi niMi

Mw Distribution ratio
Mw Mn , 1
Mn

Mw = 1, the polymer is homogeneous & contains polymers of same chain length

Mn

> 1 The degree of heterogeneity of the polymer

 Classification of polymers
1. Origin of the polymer
-Natural -Synthetic (man made)
Starch, cellulose, protein,silk, polyethene, polystryene,
jute,wool rubber PVC, bakelite

Some polymers are semi-synthetic polymers which are modified natural polymers,
cellulose acetate & cellulose nitrate.

2. Nature of the chemical reaction

Addition Condensation
•Olifinic monomer (=) *two different monomers
• no elimination of by-product *elimination of by-product
•DP x Mr of monomer *DP x Mr of repeating units
e.g PVC , polyethene ,plexiglass e.g nylon, polyester , bakelite
3. Structure and end use
Elastomers Fibers Resins plastics
Large elongation Thin thread -like Low molar mass in Polymers:
when stretched, liquid or semisolid Molded into desired
retain their shape on form. articles by
releasing force. Temperature&
pressure

Polymer chain is No. deformation. They may undergo

long & coiled and Long chain molecular further
in between chains strains held together polymerization
only weak force of by H-bonding. ---plastics (HMM)
attraction .

Flexible. Rigid. Intermolecular Intermolecular

Intermolecular force intense. Fit. force are neither
forces low, chains Crystallinity high nor low.
do not fit . permanent Rigidity, stability,
mechanical
Pg 228 strength at T &P.

Natural rubber, Wool, silk, cotton , Phenol – PVC, Plexiglass,

Buna-S rubber nylon ,terylene, formaldehyde PMMA
polystryene resin, urea
3. Structure and end use

Elastomers Fibers Resins plastics

 Types of polymerization
•Addition polymerization
•Condensation polymerization
Mechanism of free radical addition polymerization

Free radical
-Simply a molecule with an unpaired electron.
-To gain an electron, polar, highly reactive
-Breaks the bond another molecule by stealing an electron, leaving that
molecule with unpaired electron. (another free radical)
-The stability of’ º’ to react with other compounds.
unstable ------ combine with many different molecules
Stable ------- not easily combine
-Depending on the properties of the molecule
-Active center -------- location of the unpaired electron on the radicals
(there is a reaction take place)
-In F.R polymerization ----- radicals attacks one monomer electron migrates
to another part of molecule repeated. (active center moves down the chain)
 Polymerization of ethylene ( Addition polymerization)

A polymer formed by direct addition of repeated monomers without

the elimination of bye-product is called an addition polymer.
Mechanism of free radical addition polymerization
Three major steps
1. Initiation
2. Propagation
3. Termination
Initiation
Step 1. R - R 2R° endothermic reaction
R= peroxides, azocompounds or peracids

Step 2. R° + CH2 = CH2 R - CH2 - ºCH2

free
radicals ethylene monomer free radicals
exothermic reaction

Energy of endothermic < energy of exothremic

 Propagation

R-CH2- CH2° + CH2 = CH2 R- CH2 - CH2- CH2- CH2°

monomer free Dimmer free radical
radical

R- CH2 - ( CH2 )n - CH2 - CH2°

polymer free radical

Chain extension

Energy of exothermic reaction

Termination

By coupling of one polymer free radical with another polymer free

radical or initiator free radical to form stable dead polymer.

R-(CH2 ) n1 - CH2 - CH2° + R-(CH2 ) n2 - CH2 - CH2°

R-(CH2 ) n1 - CH2 - CH2 - CH2 - CH2 (CH2 ) n2 - R
Dead heavy polymer Energy of exothermic reaction
By disproporation of two polymer free radicals, a H atom attached to
one of the free radicals is shifted to other intermediate polymer;
two dead polymers, one unsaturated and other saturated are formed.

R-(CH2 ) n1 - CH2 - CH2° + R-(CH2 ) n2 - CH2 - CH2°

CH- CH°2
H

R-(CH2 ) n1 - CH2 - CH3 R-(CH2 ) n2 - CH = CH2

Saturated polymer Unsaturated polymer
Copolymerization (addition polymerization)
 A specific type of addition polymerization process
 To get the desired polymer product (different type of monomer)
 Polymer products have unique properties of monomers
 Enhanced or improved by selecting different types of monomers

Co-polymer
•A mixture of two polymers
•Consists of at least two types of repeating units

Copolymers can be classified on how these units are arranged along the chain

Random copolymer –A-A-A-B-B-A-B-A-B-A-A-A-B-B-B-

Alternative copolymer -A-B-A-B-A-B-A-B-A--A-B-A-B-A-B-A-B-A--
Block copolymer -A-A-A-A-A-B-B-B-B-B-B-A-A-A-A-A-B-B-B-B-B-B-
Graft copolymer -A-A-A-A-A-A-A-A-A-A- A-A-A-A-A-A-A-A-A-A-

B-B-B-B-B-B-
Condensation polymerization
A polymer formed by the condensation of two or more monomers
(similar or different) with the elimination of molecules like water ,
hydrogen chloride, ammonia alcohol etc. is called condensation
polymerization.

The monomers for condensation polymerization have two main

characteristics:

-Functional groups (-OH, -NH2, -CO, -COOH)

-Each monomers has at least two reactive sites. (two fictional groups)
e.g condensation polymerization
polyester
O O O“ O“
“ “
HO –C- -C –OH + HO- -OH HO –C- - C –O- -OH

Ester linkage
Dicarboxylic acid Diol Polyester (PET)

Uses:

Fibers, clothing soft-drink bottles, magnetic tape, plastic products

Polyamide

HOOC-(CH2)4-COOH + H2N - (CH2)6- N H2 OC-(CH2)4-CO- HN - (CH2)6-NH-

Adipic acid Hexamethylene

diamine Amide linkage
Nylon 66

Uses:

Tooth brushes, ropes, carpets, clothing

MONOMER MONOMER POLYMER LINKAGE TYPE

Adipic acid Hexamethylene Nylon 66 amide condensation

diamine
Dicarboxylic acid Diol polyester ester Condensation
Characteristic of condensation polymers

Condensation polymer forms slower than addition polymer forms

( heat stop: reaction stop) free radical -------- continue reaction

Condensation polymer + condensation polymer ------- rigid (chain linkage)

(extremely tough and resistant clothing)

Addition polymers ------- soft ( no active sites)

Difference between addition and condensation
polymerization
Addition polymerization Condensation polymerization
1. It demands the presence of multiple 1. Both ends of the monomer should
bond in the monomer. posses two reactive functional groups.

2. It prefers the presence of multiple 2. Minimum of two different monomers

bonds in one or more monomer. with functional groups.
3. No elimination of by-product like water. 3. It is always associated with the
elimination of water, ammonia, hydrogen
chloride etc.
4. A thermoplastic is obtained which is a 4. Thermosetting or thermoplastic
homo chain polymer. heterochain is obtained.
5. It is observed that chain growth is at 5. Chain growth is observed at two active
one active center. center.
Methods of polymerization
Methods of polymerization ( free radical polymerization)

Bulk polymerization

Solution polymerization

Suspension polymerization

Emulsion polymerization
 Bulk polymerization

Monomer + initiator Mixed Homogenous mixture

(liquid) Thermally or
photochemically

Agitated The reaction Condition Maintained Pure

heated (exothermic) temperature polymer

Monomer + Initiator Polymer

(liquid) (pure form)
Advantages Disadvantages
•Is very simple and needs simple equipments •Viscosity increases rapidly and agitation
•% conversion is high becomes difficult
•Pure and has high optical clarity •Difficult to control DP
•explosion

Uses : Plexiglass , PVC

 Solution polymerization
The monomer & dissolved solvent form Homogenous mixture
initiator
In the solution
Polymerization Polymer
∆ temperature
Isolated by
Agitated constantly
evaporating
the solvent

Monomer + Initiator T Polymer

(homogenous solution in solvent) P (pure form)
Advantages Disadvantages
•Increases in viscosity is negligible •To get pure polymer, evaporation solvent is
•agitation and heat control are easy required.
•Costly ( it uses solvent)
•High molecular mass cannot be formed
( solvent molecules may act as chain
terminators)
Uses : manufacture of polyethene, PVC
Suspension polymerization
Solvent : water ( prevented for costly solvent)

Monomer suspended (in water) continuous droplets prevented coalescing

(water insoluble) agitation

by Small quantities water soluble polymer initiator added

polyvinyl alcohol (soluble only in monomer) heated

Polymer
(dissoluble in water , spherical pearls or beads ) pearl polymerization
Monomer + initiator T Polymer
Suspension soluble P (pure form)
in water in monomer (heterogonous mixture)

Advantages Disadvantages
•Cheap •Only water insoluble monomers
•Viscosity increase is negligible •Difficult to control the polymer size
•agitation and thermal control are easy
•Product is insoluble in water
•pure Uses : manufacture of polyacetate,polystryene,
PVC
Emulsion polymerization
Water insoluble monomers
Emulsion is the colloidal dispersion of tiny droplets of a liquid in another liquid with
which it is immiscible.
Small amount of an emulsifier is required ( to maintain the system stable).

e.g soap and detergents ( normal emulsifiers and act as good surfactant)

Soap [RCOONa] detergent [RSO3Na] in water ----- RCOO- , RSO3-

Long chain non-polar ---- R
Emulsifier insoluble liquid as uniformpolar --------COO , SO3-
-
emulsifier droplets
After emulsification , water-soluble initiator is added and the system is kept agitated
at the required temperature.

The polymer formed is in the form of latex. It is isolated by coagulation by using an

electrolyric or by freezing.
Monomer + water + emulsifier+ initiator agitation polymer
(insoluble in water)
Mechanism of emulsion polymerization
Mechanism of emulsion polymerization

Formation of emulsion
Advantages

•Rate of polymerization is high

•Polymer with higher molar masses are formed
•Thermal control and control over polymer molar mass is possible
•No viscosity built up and hence agitation is easy

Disadvantages

•Polymer contain emulsifier & coagulant as impurities

•Needs further purification
Bulk Solution Suspension Emulsion
polymerization polymerization (Pearl) polymerization polymerization

M (l) + I P M+ I P Monomer: water M : water insoluble

( pure) ( pure) insoluble Solvent: water
Dissolved in solvent Solvent: water Initiator: water
(homogenous form) Initiator: only soluble in soluble
monomer Surfactants ; detergent
miscelle

Adv: Adv: Adv: Adv:

•Simple •Viscosity control •Cheap •Rate of polymerization
•% •Aagitation easy •Product isolated •High molar mass
•Pure & high •pure •Viscosity negligible •Viscosity neglet
•Agitation & thermal •Agitation easy
control are easy •Thermal control
•pure

Disadv: Disadv: Disadv: Disadv:

•Viscosity •Solvent cost •Only for water insoluble •Needs for further
•Not control DP •No high molar mass monomer purification
•explosion (solvent as chain •Difficult to control the •(emulsifiers and
transfer) polymer size coagulant as impurities)
•evaporation

Uses ; PVC, Uses ; PVC, Uses ; PVC, Uses ; PVC, PMMA,

plexiglass polyethene polystryene elastomers, polyvinyl
Polyvinyl acetate acetate
Glass Transition Temperature , Tg
 Glass Transition Temperature , Tg
Viscous liquid Both segmental & molecular motion
Visco fluid state Flow temperature
Only mixture ( no sharp mpt)
Tf

Rubbery state
(soft, flexible) Segmental motion
(visco elastic state) not Molecular motion

Tg

Glassy state : Segmental motion No

amorphous polymer Molecular motion
(hard , brittle plastic) Rigid solid
(frozen state)
Factors that affect the value of Tg

1. Crystallinity

Crystaline polymer arranged regular parallel fashion

Each chain bound strong force ( H- bonding)

Therefore, crystalline Tg > amorphous Tg

2 Molecular mass MM Tg

3 Side chain present Side chain Tg Hinder free rotation

4. plasticizers Plasticizers Tg Impurities on mpt

5. Stereo regularity Stereo regularity Tg

Tg isotactic > syndiotactic > atactic

Importance of Tg Value

Tg is not only measure of flexibility of a polymer but also gives thermal expansion,
heat capacity, electrical and mechanical properties of the polymer.

Thus, workability and usefulness of a polymer over a range of temperature can be

obtained from its Tg.

7.6 Structure and property relationship of polymer

The properties like crystallinity , tacticity, tensile strength, elasticity, resistance to chemicals,
wear and tear etc. depends on the structure of polymers.

It is very important topic polymer science.

Crystallinity of polymer
polymer ----- crystalline ; molecules are arranged in an orderly , systematically
higher force of attraction
Any polymer---- definite % of crystalline parts and amorphous parts

Degree of crystallinity depends on how polymers closely packed.

Crystalline regions of a polymer ------ individual chains are linear (without branching, bulky
substituents), losely arranged // to each other

The strains of polymer may be held ---- Vander Waal’s force , hydrogen bonding or polar interacti

Polymer with high degree crystallinity HDPE,isotactic & syndrotactic polypropenes, PVC
•High tensile strength
•Impact and wear resistance
atactic polypropenes, PVC, polystyrene
•High density and high fusion temperature
•High Tg and melt viscosity
•Stero regular arrangement of their pendent group

Characteristics of crystalline polymers are

•High density
•Hard but brittle and strong
•Solubility and permeability decrease with increase in crystallinity
2. Impact and tensile strength of polymer and molar mass

Mechanical properties of polymer : density, melt viscosity , impact and

tensile strength influenced by molar masses of polymers.

Melt, viscosity ( low molar mass) low

Molar mass viscosity
Tensile strength and impact strength molar mass 2000 DP
Beyond molar mass 2000 DP --- increase is negligible
Each polymer has a limiting molar mass at which its tensile strength and workability
are good.
3. Plastic Deformation ( Rheology) of polymer

Thermoplastics : on heating to their Tg or pressure -----

flexible and rubbery ---- deformation.
On further heating( beyond their flow temp:) :
viscous liquid to flow
on cooling ; they turn to their original state.
( this property used in moulding of thermoplastic)

Thermosetting : no deformation . First soften and then hard mass.

On further heating – no change and charring.
( primary bonds cannot be easily broken by heat.)
4. Chemical Resistivity
Attacked by a reagent, it becomes softening , swelling and losses strengt

Chemical resistivity depend on

•Presence or absence of residual unsaturation
•Presence or absence of polar groups
•Molar mass, degree of crystallinity and extent of cross linking
Polymer swelling non-polar solvent
(non-polar groups) dissolution (benzene, toluene, CCl4)
H/C polymer

Polymer soluble polar solvent

(polar groups) (water, alcohols)
( -OH gps or -COOH)
Polymer hydrolysis strong alkali (at high temp)
(ester gps)
polyester

Polymer hydrolysis strong acid or alkali (at high temp)

(nylon)
polyamide

Polymer degradative oxidation

(Unsaturated residue)
(natural rubber & some synthetic rubber) in the air in light or ozone

(Natural some synthetic rubbers undergo degradative oxidation in air)

Poly alkenes, PVC, fluorocarbon ------ high degree of chemical resistance.

Molar mass crystallinity chemical resistivity

So, linear polymer < branched and cross –linked polymer

5. Tacticity of Polymers
Polymer molecules have different arrangement of adjacent chiral centers within molecules

Actactic useless gummy solid

Isotactic crystalline , tough
6. Viscoelasticity of polymer

Few polymeric materials exhibits both viscous and elastic characteristics under conditions.
Viscoelastic materials have elements have on both properties and exhibit time dependent strain

Elasticity: bond stretching along crystallographic planes in an ordered solid.

Viscoelasticity : the diffusion of the atoms or molecules inside of and amorphous
material.
Physical state of polymer are dependent on their chain length and molecular weight.
Elastic solid or viscous liquids depending on their physical state.
The change of physical properties of polymer is due to the effect of temperature.

They transform to hard and brittle when cooled slowly or vice versa.
The rate of cooling affects the properties of polymer.
7.7. PLASTICS
-macromolecules, formed by polymerization and having the ability to be shaped by
the application of reasonable amount of heat and pressure or some other form of
force. Or pg 216
A plastic material should posses sufficient rigidity, dimensional stability and
mechanical strength at room temperature as a useful house hold articles, gadge or
structural part.

Depending on the nature and properties , polymers are classified as

(i) Plastics (ii) Elastomers or rubbers (iii) fibers

7.7.1. Types of plastics

1. Thermoplastics
 Polymers, flexible, linear chain molecules, which one shaped or formed, can be
reshaped repeatedly, till it loses its property.
 crystalline or amorphous e.g polyethene, polypropylene, nylon , polycarbonate
2. Thermosetting
 rigid three dimensional net work polymers, which one shaped ,cannot be softened by
the application of heat.
 Excess heat will char the material.
 e.g phenol formaldehyde, urea formaldehyde, malamine formaldehyde, thermosetting
polyester.
Synthesis of Polyethylene (polythene)

Simplest homopolymer
Simplest and most inexpensive polymers
Waxy, chemically inert plastic.
Thermoplastics formed by the addition polymerization ethylene.
Two types of Polyethylenes :
(i) Low density polyethylene LDPE (ii) High density polyethylene HDPE
(i) Low density polyethylene LDPE

350°C , 1000 - 2500 atm

n [CH2 = CH2] [ CH2 CH2 ] n
Ethene O2 or peroxide catalyst chain polymerization polyethene

(ii) High density polyethylene HDPE

TiCl4 + Al(C2H5)3 [ CH2 CH2 ] n

n [CH2 = CH2]
Ethene
Zeigler natta catalyst at 50-70°C polyethene
(coordination polymerization)
Properties and application of LDPE and HDPE

Property LDPE HDPE

Structure Linear structure with Linear polymer with
extensive branching minimum branching
Degree of crystallinity Low (40%) High (90%)
Melting point Low 110°C Higher 140°C
Density Low 0.912 to 0.935 High 0.96 to 0.98
Tensile strength Low low
Stiffness and Low high
hardness
Chemical resistivity Low swells and High does not swell
dissolves in or dissolves in
hydrocarbon solvents solvents
Application In films, sheets In moulded articles
Polytetrafluoroethylene - PTFE (Teflon)

Peroxide (initiator)
n [CF2 = CF2] [ CF2 CF2 ] n
tetrafluoroethylene
Emulsion polymerization Polytetrafluoroethylene

PTFE (Teflon)

Properties
•Teflon is a linear polymer with high degree of crystallinity of ~ 95%
•Its flow temp: is high (327°C )
•It is insoluble in all solvent.
•It is chemically inert and not attacked by acids, alkalis, oxidizing and reducing
agents.( conc: sulphuric acid and fuming nitric acid do not have any action on
Teflon)
•It is not wetted by oil or water.
•It has high resistance to impact and wear and tear.
•It is thermally stable and has a good electrical insulating property.
Polymethyl –methacrylate ---- PMMA (Plexiglass)

CH3 CH3
Bulk / suspension
n [CH2 =C ] [ CH2 - C ]
Peroxide
COOCH3 COOCH3
MMA PMMA
n
Properties
•PMMA is a white transparent amorphous thermoplastics. It is amorphous due to
bulky pendent group ( COOCH3 ) present.
•It has excellent optical clarity and not affected by sunlight or age.
•It has excellent chemical resistivity but soluble in many organic solvent.
Polyurethane(PU)
Addition polymer
O

[ NH C O ] grouping called methane group.

Properties
•PUs are spongy transparent linear thermoplastics.
•They have low melting point and high degree of flexibility
•They are resistant to water, oil and corrosive chemical.
Polycarbonate (PC)

O O
Polyester of unstable OH-C-OH carbonic acid [-O-C-O- ] gp

Condensation polymers.

Properties
•Pcs are white transparent amorphous solids.
•They have high melting point.
•They have high tensile strength and impact resistance
•Soluble in a number of solvents.
 SYNTHESIS, PROPERTIES & APPLICATIONS OF FEW COMMERCIAL
THERMOPLASTIC AND THERMOSET
Polyethylene Poly Polymethyl Polyurethane Polycarbonates
(PE) tetrafluroethylene methacrylate (PU) (PC)
(PTFE) (PMMA)

CH2=CH2 CF2=CF2 CH2=C(CH3)- Polyester of

COOCH3 [-NH-C-0- ] ---- unstable
methane gp OH-C-OH carbonic
acid
[-O-C-0- ] gp

Addition polymer Addition polymer Addition polymer Addition Condensation

polymer polymer
LDPE 350°C, peroxide peroxide
1000-2500 atm ,O2

HDPE 50 -70 °C, CF2=CF2 emulsion poly n Bulk/ suspension

( Zeigler natta polyn
TiCl4 + Al (C2H5)3

Insoluble in all Insoluble in all solvent. Soluble in organic soluble in a number

solvent. solvent of solvent.
Polyethylene Poly Polymethyl Polyurethane Polycarbonate
(PE) tetrafluroethylene methacrylate (PU) s (PC)
(PTFE) 7 (PMMA) 3 3 4
2
Chemically Chemically inert Excellent
inert Chemically
resistivity
Not wetted by oil optically clarity, not Resistant to
or water affected by water , oil,
sunlight/age corrosive
chemical
High resistance High tensile
wear and tear strength,
impact
resistance
Linear polymer, White transparent Spongy White
high degree of amorphous transparent transparent
crystallinity, flow ( due to bulky linear polymer amorphous
temp 327°C, pendent gp
-COOCH3-
present)
Thermoset Polymers
A high degree of cross-linking , resist deformation and solution once their final
morphology achieved.
Such polymers are usually prepared in molds that yield the desired object.
Because these polymers, one formed , cannot be reshaped by heating, they are called
thermoset.
Phenol formaldehyde, urea formaldehyde

Phenol -formaldehyde
-Oldest condensation polymer
-Phenol ring has three binding sites and one para position
-Formaldehyde has two binding sites.
-Catalysed :: H+ ions or OH- ions
The nature of product formed depend on -----
1. Relative concentrations of phenol and formaldehyde
2. H+ or OH – is used as catalyst.
 Two intermediates are NOVOLACS and RESOLS ----
linear polymers ---low molar masses, fusible and soluble in organic solvents;

Bakelite ----extensive branching --- highly cross linked insoluble, hard rigid
polymer.
Same rigid three dimensional network

Novolacs ---- in acidic catalyst------ P:F > 1

Resols --- in basic catalyst ------ P:F < 1

Properties

•N& R have adhesives properties,

• soluble in Organic solvents.
• After curing , they form hard, rigid insoluble cross-linked polymer
--- Bakelite
Distnction between thermoplastics and thermosetting

thermoplastics thermosetting
Addition polymerization condensation polymerization

Linear polymer 3D network structure

bifunctional Higher functional

Low MW High MW

Soft, weak and brittle Hard, strong and brittle

Soluble in organic solvent insoluble

Softened on heating readily Do not softened

Can be softened, reshaped,
Retain the shape and structure
recycled
Techniques of plastic moulding
 Techniques of plastic moulding
1. Compression moulding
2. Injection moulding
3. Blown film Moulding
4. Extrusion Moulding
 Compression moulding
• Process for forming thermosets by applying heat and pressure.
• A measured amount of thermoset powder, granules or pellets, is fed
into the mold cavity.
• Heat softens the material and pressure fills the cavity, then the
material is cured.
• They process is of limited use for thermosets because of the cooling
time required of the mold.
• Typical products include electrical insulators, pot handles,
• automotive parts
 Compression moulding
• thermoset
• Powder, granules or pallets –fed -- mould cavity
• Heat softens materials
• Pressure -----curved
• Heat ---- transform ---highly cross-linked & network
structure
• limited use-----Cooling time
• Electrical insulators, pot handles ,automotive parts
 Injection moulding
• Thermoplastics
• However , with the development of the reciprocating screw type
equipment, thermosets can also be injection molded.
• The basic process includes plasticizing, injection, cooling and
ejection.
• Granules are from a hopper into a srew that rotates to feed the
material into a heated chamber to allow the material to change
into a molten state.
• The material is then forced through a nozzle into the mold cavity.
• A cooling time is necessary to allow the polymer to become
solid ,and is then ejected from the mould by mechanical ejector
pins.
 Injection moulding unit
• Thermoset, thermoplastics
• Reciprocating screw type:
• plasticizing, injection, cooling, ejection.
• Granules (hoppers) – rotates ---heated chamber----
molten states
• Material –forced--- nozzle---molten cavity
• Cooling time—solid --- ejected by mechanical
ejector pins
• Toy made from high impact polystyrene (HIPS)
 Blown film Moulding
• A combination of extrusion, blow molding and calendering.
• As material is extruded, air is forced through the center of a
die, causing the material to expand to the diameter of the
mold.
• Mold is open at the end, and the material is continuously
taken up on rollers.
• During the take up process, the walls on the “tube may be
seamed welded and perforated such as the case with garbage
bags.”
• Used to produce thin film hollow tubes.
 Blown film Extrusion Moulding
• thermoplastics
• Extrusion, blown molding ,calendaring
• Extruded, air is forced through center of die,
expand to diameter of the mold.
• Mold is open at the end, rollers .
• Tube –welded and perforated
• Thin film hollow tubes, HDPE, LDPE
 Extrusion Moulding

• Continuous flow of molten material is forced through a die

• Shape of the final product is determined by the shape of the
die opening.
• Thermoplastics material is fed from a hopper, similar to the
configuration of the screw system in the injection molding.
• The screw forces the material through a tapered opening in
the die.
• Heat and friction causes plasticizing to occur, softens the
material and forces it through the doe opening.
• Materials is cooled by either air or water.
 Extrusion
Advantages
• Rate of cooling can be controlled and further forming is
possible.
• E.g ,PVC pipe is extruded as electrical conduit. If allow to
be immersed in hot water conduit can be bent at 90°
angles.
Uses
• Products that are extruded include tubing, rods, bars,
moldings, sheets and films.
• Extrusion is also used for coating wire and cable.
 Extrusion Moulding

• thermoplastics
• Shape of final product --- the shape of the die opening
• ~ injection
• Screw forces the material through a tapered opening in the
die
• Heat and friction ---plasticizering , softens , forces
• Cooled by air or water
• Tubing, rods, bars, moldings, sheets and films
• Coating wire and cable
• PVC pipe as electrical conduct. Hot water , can be bent at 90°.
 Elastomers
• Elastomer is defined as a long chain polymer which under
stress undergoes elongation by several times and regains its
original shape when the stress in fully released.
An elastomer’s characteristics:
• It should have a linear but highly coiled structure.
• Inter chain cohesive forces should be negligible
• It should undergo elongation under stress and
• Regain the original size when the stress in fully released.
• E.g natural rubber, all synthetic rubbers, some nylon
matreials.
 Natural Rubber
• Rubber is obtained from rubber trees usually
grow in tropical regions.
• The tree stores rubber as a milky white fluid
called latex behind the bark of the tree.
• When a cut is made on the bark the liquid
oozes out and collects in vessels kept for the
purpose.
• Is an addition polymer formed
CH3

CH2 = C – CH = CH2 Isoprene ( 2 methyl 1,3 butadiene)

DP of rubber is 5000.

CH3 CH3

CH2 = C – CH = CH2 + CH2 = C – CH = CH2

CH3 CH3 polymerization

Rubber
-CH2 – C = CH - CH2- CH2 – C = CH - CH2- polyisoprene
1,4 di -isoprene
• Poly isoprene can exist in 2 isomeric forms cis and trans.
• Natural rubber is the cis isomer while trans isomer is called
gutta –percha.

CH3 H CH3 CH2--------

C = C
C = C
--------CH2 CH2--------
--------CH2 H

CIS polyisoprene TRANS polyisoprene

Natural rubber Gutta-percha
 Deficiencies of natural rubbers
• addition product of isoprene units and still contains
a large number of double bonded carbon atoms.
•At low temperature it is hard and brittle but as temperature rises it
becomes soft and sticky.
•It gets easily air oxidized and produces a bad smell even if kept as such
for a few days.
•It is soluble in many organic solvents.
•It absorbs large quantities of water.
•Its chemical resitivity is low and is attacked by acids alkalis, oxidizing
and reducing agents.
•Its tensile strength , abrasion resistance , wear and tear resistance are
low.
 Comparison of properties of material and synthetic
rubber
Property Natural Rubber Synthetic Rubber
Tensile strength Low High
Chemical resistivity Low – gets oxidized even High – not oxidized in air
air
Action of heat Cold condition it is hard Can withstand effect of
and brittle, at higher heat or range of
temperatures soft and temperature
sticky
With organic solvents Swells and dissolves Does not swell and
dissolve
Ageing Undergoes ageing quickly Resists agening
Elasticity On increased stress Has high elasticity
undergoes permanent
deformation
Vulcanisation
 Vulcanization
• Is a process (heating natural rubber with S at
135°C and (1-4 hours)
• To improve the properties of natural rubber
• ‘S’ atoms form bridges between poly neoprene
chains (a part of double bonded carbon atoms)
• Degree of vulcanization ∞ the amt of ‘S’ added
• S Tensile stregth, chemical resistance and
wear and tear resistance
• Tyre ---3-4% S , filler--- C are added
• 30% S----full saturation ---a rigid non flexible
rubber ( ebonite)
 Synthetic Rubbers
• Buna-S Rubber
• Neoprene Rubber (Chloroprene Rubber)
• Butyl Rubber
 Buna-S Rubber

• Co-polymer formed
• 1,3 butadiene + styrene
• Emulsion polymerization
• Peroxide catalyst at 50°C
• Buna-S Rubber
• Bu ---butadiene
• na--- sodium (catalyst)
• S --- stryene
• SBR (Stryene butadiene rubber) or Cold rubber -
contains unsaturation & Vulcanized with ‘S’
• Uses --- tyre treads and shoe soles
 Buna-S Rubber
C6H5

• n CH = CH2 + n CH2=CH - CH = CH2

Styrene 1,3 butadiene
C6H5

Buna-S Rubber
( CH - CH2 - CH2-CH = CH – CH2 ) n
 Neoprene Rubber
• Chloroprene rubber
• 2 chloro 1,3Catalytic
butadiene
HCl
• Acetylene dimerization vinyl acetylene
2-chloro 1,3 butadiene(neoprene or chloroprene)
(monomer)

• Emulsion polymerization, peroxide

• Vulcanized using ZnO
• Conveyour belts, hoses
 Neoprene Rubber
• CH CH + CH CH CH C CH CH2
acetylene Vinyl acetylene
Catylytic dimerisation
CH C CH CH2+ HCl CH2 C CH CH2
Cl
2-chloro 1,3 butadiene

nCH2 C CH CH2 ( CH2 C = CH CH2 )n

Cl Cl
2-chloro 1,3 butadiene poly 2-chloro 1,3 butadiene
 Butyl Rubber

• Copolymer
• isobutylene + isoprene (1 to 5%) at 90°C
CH3 CH3
nCH2 = C
+ n CH2 = C - CH =CH2
CH3
isobutylene isoprene
CH3 CH3 CH3

[ CH 2 - C - CH2 - C = CH -CH2 - CH2 - C ]n

CH3 CH3

Butyl Rubber
Buna-S Rubber Neoprene Rubber Butyl Rubber

1,3 butadiene + 2 chloro 1,3 isobutylene +

styrene butadiene isoprene

SBR (Stryene Chloroprene rubber

butadiene rubber)
or Cold rubber
 Properties
• Chemically inert
• Permeability to air, about 10% that of natural
rubber
• Good resistance to heat, abrasion and wear
• Soluble in benzene
• Not easily attack by ozone
• Good electrical insulating characteristics