Polymers

Dr. Druman Utekar

 Definition
• Polymer is high molecular weight substance
formed by joining a large number of small
repeating units called as Monomers.

• In Greek language poly means many & mer means units

• Polymers form very important components in our daily life. The polymers are
highly useful in domestic industrial & medical fields.
 Examples
• Rubber
• Polyethene, nCH2=CH2 polymerization (CH2 – CH 2) n

• Polypropylene
• Teflon
 The following are the reasons for the extensive use of
polymers.

• Most of the polymers are non-toxic & safe to use.

• They have low densities (light in weight) so transportation polymers will be easy.
• They posses good mechanical strength.
• These are resistant to corrosion and will not absorb moisture when exposed to the
atmosphere.
• These can function as good thermal & electrical insulators.
• These can be moulded and fabricate easily.
• They possess aesthetic colors.
But the limitations for the use of polymers are

– Some polymers are combustible.

– The properties of polymers are time dependent

– Some of them cannot with stand high temperature.

 Classification of polymers
A) Based on source
B) Based on Physical State
Amorphous and semi crystalline
C) Based on Thermal Behavior or Response to
Heat.-
D) Based on end use.-Fibres, Plastics, Elastomers,
Films, Paints, Adhesives
E) Based on Origin
F) Based on Tacticity
 Classification of polymers
G) Based on Conductance
H) Based on Environment Friendly Nature
I) Based on the type of monomers
J) Based on Number of Monomers
K) Based on Chemical Nature
L) Based on Growth Mechanism of
Polymerization
 Based on Tacticity
• The arrangement of functional groups on carbon backbone of the polymer is
called Tacticiy.
• It is manly divided into 3 types.
1) Isotactic polymers: Those polymers in which the functional groups are arranged
on the same side are called Isotactic polymers. E.g.:- PVC
2) Atactic polymers: When there is no regular arrangement of functional groups on
the back bone of the polymer chain these polymers are called atactic polymers.
E.g.: PVC (Poly Vinyl chloride)
• Syndiotactic Polymers: The polymers with alternate arrangement of functional
groups are called syndiotactic polymers for e.g.:- PVC
Difference between condensation and addition polymerisation:-
Condensation polymerisation Addition polymerisation

(1) It is also known as step growth (1) It is also known as chain growth
polymerisation polymerization

(2) It takes place in monomers having (2) It takes place only in monomers
reactive functional groups having multiple bonds.

(3) It takes place with elimination of (3) It takes place without elimination of
simple molecule like H2O,NH3,HCl simple molecule.
etc.,

(4) Repeat units of monomers are (4) Repeat units & monomers are same.
different

(5) The polymer is formed in gradual (5) Reaction is fast and polymer is formed
steps at once.

(6) The molecular mass of polymer (6) There is very little change in the
increases throughout the reaction molecular mass throughout the
reaction

(7) Product obtained may be (7) Product obtained are thermoplastic

thermosetting/thermoplastic

(8) E.g.:- Bakelite, polyester ,polyamides (8) E.g:-Polyethylene, PVC, poly styrene.
etc.,
 Difference between thermoplastic & thermosetting resins: -
Thermoplastic resins (or) Polymers Thermosetting resins

(1) These are produced by addition (1) These are produced by

polymerization condensation polymerization.

(2) The resins are made of long chains (2) The resins have three dimensional
attached by weak Vander Waal’s network structure connected bonds.
force of attraction

(3) On heating they soften and on (3) On heating they become stiff &
cooling become stiff chemical hard. No change on cooling.
nature won’t change. Chemical nature changes.

(4) They can be remoulded (4) They cannot be remoulded because

once set means they are
permanently set

(5) Scrap (waste product) can be used (5) Scrap cannot be used

(6) The resins are soft, weak and less (6) The resins are usually hard, strong
brittle tough & more brittle

(7) These are easily soluble in some (7) Resins are not soluble in organic
organic substances Solvents
E.g.:- PVC, polyethylene etc., E.g.:- Nylon, Bakelite etc.,

(8) Contain long chain polymer with no (8) They have 3D network structure.

cross linkage.
 Molecular Mass of Polymer
• The molecular mass of polymer is an important property of
polymer because many important properties are influenced by
molecular mass. Polymers with higher molecular mass are tougher
and more resistant. Their viscosities and softening temperature are
also higher. Thus polymers with molecular mass are often required
for particular purposes.
• Molecular mass of polymer is not a fixed or constant value like
organic compound. Their molecular mass is controlled by
polymerization reaction, which in turn depend upon availability of
functional group, charge carrier, life time of charge carriers.
Because of random nature of growth process, the product of
polymerization process is mixture of chains of different length.
• Hence polymers are poly disperse mixture of various
molecular mass polymers. Therefore molecular mass of polymers is
average molecular mass.
Average molecular mass of polymers can be
expressed in following ways
• __
1. Number Average Molecular Mass (Mn)
2. Weight Average Molecular Mass (Mw)
3. Z-Average Molecular Mass (Mz)
4. Viscosity average Molecular Mass (Mv)
 Methods for determining the
molecular weights of polymer
A) Primary or Absolute methods, which are
capable of determining molecular weights from
first principles like colligative property
measurements(Which gives Mn) , light
scattering measurements (which gives Mw)
B) Secondary or relative methods, Which
require calibration with samples of known molar
mass. Examples Viscosity measurements which
gives Mv.
 Number average Molecular Mass (
Mn)
In this number of molecules are involved in the molecular weight measurements.
Hence the molecular weight is obtained by colligative property measurements and
known as number average molecular weight.

Let us consider N1,N2, N3….. be the number of molecules of polymer in a sample solution.
And M1, M2, M3 …be the their molecular weight then Number average molecular weight
is given by

Polymer solution Number of Their molecular

of polyethene molecules weight
Sample has 100 N1 150 M1
200 N2 200 M2
300 N3 300 M3
Weight Average molecular Weight
• Let us consider N1,N2, N3….. be the number of molecules of polymer in a sample
solution.
• And M1, M2, M3 …be the their molecular weight
• And W1, W2, W3 …be the their weight(mass) then Weight average molecular
weight is given by

Polymer solution Molecular weight Their weight

of polyethene
Sample has 100 15g
200 20g
300 30g
 Z-average molecular Weight
Let us consider N1,N2, N3….. be the number of molecules of polymer in a
sample solution.
And M1, M2, M3 …be the their molecular weight, then Z-average molecular
weight is given by
Viscosity Average molecular weight
• By Mark Howick Equation
 Compounding of Plastics
• In order to impart certain definite properties
to the finished products, resins are
compounded with certain other substances.
The process is called as compounding of
plastics.
 1. Binders or Resins
• The product of polymerization is called resins and this
forms the major portion of the body of plastics.
• It is the binder, which holds the different constituents
together.
• Thermosetting resins are usually, supplied as linear –
polymers of comparatively low molecular weight, because
at this stage they are fusible and hence, mouldable.
• The conversion of this fusible form into cross-linked
infusible form takes place, during moulding itself, in
presence of catalysts etc.
• A binder may compose of 30-100%.
• The binders used may be natural or synthetic or cellulose
derivatives.
 2. Fillers
• Fillers are generally added to thermosetting
plastics to increase elasticity and crack resistance.

• Fillers improve thermal stability, strength, non

combustibility, water resistance, electrical
insulation properties & external appearance.

• E.g.:- Mica(Hardness), cotton(Shock resistance) ,

carbon(electrical conductivity) black, graphite,
BaSO4 etc. Asbestos ( Heat resistance)
 3. Plasticizers
• Plasticizers are substances added to enhance the
plasticity of the material and to reduce the
cracking on the surface.
• Plasticizers are added to the plastics to increase
the flexibility & toughness. Plasticizers also
increase the flow property of the plastics.
• Commonly used plasticizers are vegetable oils,
camphor, esters of steric, oleic acid, tributyl
phosphate, triphenyl phosphate etc.
 4. Dyes and Pigments
• These are added to impart the desired colour
to the plastics and give decorative effect.

• e.g.:-Inorganic Pigments: Lead chromate

(yellow), ferro cyanide (blue)
• Organic Pigments: Alizarin Red, Indigo Dye,
Azo dyes.
 5. Lubricants
• Includes Oils, waxes and soaps.
• They help in easy moulding and glossy finish
to final product.
• The lubricant prevent the plastic materials
from sticking to the mould.
 6. Catalysts
• They are added to plastics to accelerate
polymerizations reaction.
• ZnCl2, CaO, ammonia, benzoyl peroxides
 7. Stabilizers
• They are added to improve thermal stability
during processing. Eg. Polymers of vinyl chloride
show a tendency to undergo decomposition at
moulding temperatures. So during their moulding
heat stabilizers are added.
• i) Opaque moulding stabilizers: Salts of lead, like
white lead, lead chromate, red lead, lead silicate
etc.
• Ii) Transparent Moulding stabilizers: Stearates of
Lead, chromium and barium.
• In addition small quantitates of antioxidants,
antiseptics, fungicides, flame retardants etc.
are added as ingredient of plastics.
 FABRICATION OF PLASTICS
• Giving any desired shape to the plastics (granules or powders)
by using mould under the application of heat and pressure.
• A proper method is to be selected depending on the shape
and type of resin used.
• Methods involves partial melting of resinous mass by heating.
• In case of thermo-plasts molten resin is introduced in
die/mould and desired shape could be achieved by
compression and further cooling.
• In case of thermo-sets partially polymerized mass or raw
materials are introduced in the die/mould, which further
cured at high temperature in the mould itself to achieve
desired shape.
1. In case of thermoplasts, curing is done at room temperature
(low temperature)
2. In case of thermosets, curing is done at high temperature to
obtain desired cross-linking
 TYPES OF FABRICATION

• [I} Compression Molding (Suitable for Thermosets /

Thermoplasts)
• [II] Injection Molding (Suitable for Thermoplasts)
• [III] Transfer Molding (Suitable for Thermosets)
• [IV] Extrusion Molding (Suitable for Thermoplasts)
 COMPRESSION MOULDING

1. Common and oldest method for molding thermosetting / thermoplastic materials

2. Compression of raw materials or soften resinous mass is done in the mould /die
under heat and pressure
 COMPRESSION MOULDING
1. Predetermined quantity of raw materials is introduced carefully in the mould,
further compressed by hydraulic pressure (2000 to 10000 psi)
2. Molten or soften resinous mass gets filled in the cavity of mould.
3. Curing is done by heating (Thermosetting) or by cooling (Thermoplastics)
4. Finally moulded article is separated from the mould by opening the mould apart.
5. Applications : Electric switch boxes, Ash trays, cabinets for radio, television,
computers etc.
INJECTION MOULDING
 INJECTION MOULDING
• This method is especially used for thermoplastic materials
• Powder or granular resin is heated in a cylinder and
injected at a controlled rate in a mould with the help of
piston plunger or screw.
• Piston plunger or screw is used to force the material in
mould.
• Pressure up to 2000 kg/cm2 (100 psi) is used
• Once the article is formed mould is cooled and half mould
is opened to remove the finished article.
• Disadvantage of the method is formation of air bubbles or
cavities in the articles
• Applications: Smaller but large volume articles such as, pen
caps, bottle caps, cups, containers, mechanical parts
TRANSFER MOULDING
 TRANSFER MOULDING
• The method combines features of both Compression Molding (hydraulic pressing
of molding materials - thermosets) and Injection Molding (ram-plunger and filling
the mold through a sprue).
• The method is used especially for molding thermosetting resins (thermosets)
• Products with relatively intricate designs could be fabricated with this method
• Powdered raw materials are heated at certain low temperature to soften and then
introduced through an orifice or sprue in the mould
• Then it is cured in the mould at high temperature for certain time
• Finally the moulded article is removed by separation of mould

Advantages:
• Articles with intricate shapes could be designed
• Aerospace and automobile parts, car body, helmets
• The articles produced are blister free
• Fine wires and glass fibers can be inserted in the mould
• Even thick pieces can be cured completely and uniformly
Extrusion Molding
 Extrusion Moulding
• Whenever continuous molding of material like wires,
cables, and sheets is required extrusion molding is
used. The thermoplastic materials are molded by this
method. They undergo continuous molding to form
articles of uniform cross section. In this method, the
thermoplastic material are heated to plastic condition
and pushed by means of screw conveyor in to a mould
cavity having required outer shape of articles to be
manufactured. Here the plastic mass gets cooled due
to atmospheric exposure. A long conveyor carries away
the cooled products continuously.
Biodegradable polymers-Polylactic acid
• Polylactic acid, also known as poly(lactic acid) or
polylactide (abbreviation PLA) is a thermoplastic
polyester with backbone formula (C3H4O2)n or [–
C(CH3)HC(=O)O–]n, formally obtained by condensation
of lactic acid C(CH3)(OH)HCOOH with loss of water
(hence its name). It can also be prepared by ring-
opening polymerization of lactide [–C(CH3)HC(=O)O–
]2, the cyclic dimer of the basic repeating unit.
• Synthesis
• The monomer is typically made from fermented plant starch such as from corn,
cassava, sugarcane or sugar beet pulp.

• Several industrial routes afford usable (i.e. high molecular weight) PLA. Two main
monomers are used: lactic acid, and the cyclic di-ester, lactide. The most common
route to PLA is the ring-opening polymerization of lactide with various metal catalysts
(typically tin octoate) in solution or as a suspension. The metal-catalyzed reaction
tends to cause racemization of the PLA, reducing its stereoregularity compared to the
starting material (usually corn starch).[7]

• The direct condensation of lactic acid monomers can also be used to produce PLA.
This process needs to be carried out at less than 200 °C; above that temperature, the
entropically favored lactide monomer is generated. This reaction generates one
equivalent of water for every condensation (esterification) step. The condensation
reaction is reversible and subject to equilibrium, so removal of water is required to
generate high molecular weight species. Water removal by application of a vacuum
or by azeotropic distillation is required to drive the reaction toward
polycondensation. Molecular weights of 130 kDa can be obtained this way. Even
higher molecular weights can be attained by carefully crystallizing the crude polymer
from the melt. Carboxylic acid and alcohol end groups are thus concentrated in the
amorphous region of the solid polymer, and so they can react. Molecular weights of
128–152 kDa are obtainable thus.
 Properties
• PLA polymers range from amorphous glassy polymer to semi-crystalline and highly crystalline
polymer with a glass transition 60–65 °C, a melting temperature 130-180 °C, and a Young's modulus
2.7–16 GPa.[13][14][15] Heat-resistant PLA can withstand temperatures of 110 °C.[16] The basic
mechanical properties of PLA are between those of polystyrene and PET.[13] The melting
temperature of PLLA can be increased by 40–50 °C and its heat deflection temperature can be
increased from approximately 60 °C to up to 190 °C by physically blending the polymer with PDLA
(poly-D-lactide). PDLA and PLLA form a highly regular stereocomplex with increased crystallinity. The
temperature stability is maximised when a 1:1 blend is used, but even at lower concentrations of 3–
10% of PDLA, there is still a substantial improvement. In the latter case, PDLA acts as a nucleating
agent, thereby increasing the crystallization rate[citation needed]. Biodegradation of PDLA is slower
than for PLA due to the higher crystallinity of PDLA[citation needed]. The flexural modulus of PLA is
higher than polystyrene and PLA has good heat sealability.

• Racemic PLA and pure PLLA have low glass transition temperatures, making them undesirable
because of low strength and melting point. A stereocomplex of PDLA and PLLA has a higher glass
transition temperature, lending it more mechanical strength.
 Uses
• Consumer goods
• PLA is used in a large variety of consumer products such as disposable tableware, cutlery,
housings for kitchen appliances and electronics such as laptops and handheld devices, and
microwavable trays. (However, PLA is not suitable for microwavable containers because of its low
glass transition temperature.) It is used for compost bags, food packaging and loose-fill packaging
material that is cast, injection molded, or spun.[35] In the form of a film, it shrinks upon heating,
allowing it to be used in shrink tunnels. In the form of fibers, it is used for monofilament fishing
line and netting. In the form of nonwoven fabrics, it is used for upholstery, disposable garments,
awnings, feminine hygiene products, and diapers.

• PLA has applications in engineering plastics, where the stereocomplex is blended with a rubber-
like polymer such as ABS. Such blends have good form stability and visual transparency, making
them useful in low-end packaging applications.

• PLA is used for automotive parts such as floor mats, panels, and covers. Its heat resistance and
durability are inferior to the widely used polypropylene (PP), but its properties are improved by
means such as capping of the end groups to reduce hydrolysis.[35]
• Agricultural
• In the form of fibers, PLA is used for monofilament fishing line and
netting for vegetation and weed prevention. It is used for sandbags,
planting pots, binding tape and ropes .[35]

• Medical
• PLA can degrade into innocuous lactic acid, so it is used as medical
implants in the form of anchors, screws, plates, pins, rods, and
mesh.[35] Depending on the exact type used, it breaks down inside
the body within 6 months to 2 years. This gradual degradation is
desirable for a support structure, because it gradually transfers the
load to the body (e.g. to the bone) as that area heals. The strength
characteristics of PLA and PLLA implants are well documented.
 Conducting Polymers
• Please see the pdf given