B.M.S.

College Engineering, Bengaluru 560 019

(Autonomous institute, Affiliated to VTU)

Department of Chemistry

Polymers for Engineering Applications 08 hours

Polymers - Introduction, Molecular weight - number average and weight average molecular weight,
Polydispersion index and its significance, numerical problems;
Glass transition temperature (Tg); Structure and property relationship in polymers;
Plastics - Definition of resins and plastics; Synthesis, properties and applications of PMMA and UF
resin;
Elastomers - Synthesis, properties and application of butyl rubber and nitrile rubber;
Polymer composites - Composites as structural material; Synthesis and applications of Kevlar and
Carbon fibers;
Conducting polymers - Introduction, synthesis and conducting mechanism of polyacetylene and
applications.
Biodegradable polymers - Introduction, Polyglycolic acid - synthesis, degradation and uses.
Self-study: Polycarbonates, Recycling of PET

Polymers
The word ‘polymer’ is derived from Greek words: poly means many and mer means unit or part.
The term polymer is defined as very large molecules having high molecular weight. These are also
referred to as macromolecules, which are formed by the joining of repeating structural units on a large
scale. The repeating units are simple and reactive molecules known as monomers and are linked to
each other by covalent bonds. The monomers are the building blocks of polymer. The process of
formation of polymers from respective monomers is called polymerization. The transformation of
ethane (ethylene) to polyethylene or the reaction of hexamethylene diamine and adipic acid leading to
the formation of Nylon 6,6 are examples of two different types of polymerization reactions.
Ex: natural rubber, polyvinyl chloride (PVC), polyethylene, Nylon 6,6, etc.

The importance of polymers in our lives is almost breathtaking. Proteins and carbohydrates are
natural polymers of high molecular weight. Nucleic acids, responsible for the transmission of genetic

1 Dr. AN, Dept. of Chemistry, BMS CE (2024-25 – II, for PD & PX)
characteristics in living organisms, are polymers. Natural rubber, synthetic elastomers (synthetic
rubbers), plastics, synthetic fibers, and resins are all polymers.
Terminologies
Polymer: “A polymer is defined as a macromolecule of high molecular weight formed by the repeated
combination of several simple molecules called monomers of one or more type through covalent
bonds” Ex: Polyethylene, nylon 6,6, PVC, Teflon, polyester, bakelite, etc.
Monomers: are small molecules that combine with each other to form polymers.
Ex: ethylene, vinyl chloride, butylene, etc.
Functionality of monomer: The number of bonding sites in a monomer molecule.
Polymerization: is defined as “the chemical reaction in which monomer is converted into polymer”
Degree of polymerization (DP): The number of repeating units (n) in the chain of a polymer is called
the ‘degree of polymerization’ (DP). DP is represented as ‘n’.
Ex: Polythene, (–H2C–CH2–)n
Classification of polymers: There are several ways of classification of polymers.
1. Classification based on structure of polymers
Linear polymers: These polymers consist of long and straight chains.
Branched polymers: These polymers contain linear chains having some branches.
Cross-linked polymers: These are usually formed from tri-functional monomers and contain strong
covalent bonds between various linear chains. e.g. vulcanized rubber, urea-formaldehyde resins, etc.

2. Classification based on the composition

Homopolymer: A polymer consisting of a single type of repeating unit.

Copolymer (heteropolymer): is a polymer derived from two (or more)

different types of monomers. Commercially relevant copolymers are ABS
plastic, nitrile rubber, and butyl rubber.
3. Classification based on the stereo-regularity
Tacticity: The orientation of monomeric units in a macromolecule can take an
orderly or disorderly fashion with respect to the chain. If all the side groups lie
on the same side of the chain (cis arrangement), it is called an ‘isotactic’

2 Dr. AN, Dept. of Chemistry, BMS CE (2024-25 – II, for PD & PX)
polymer. If the monomers have entered the chain in a random fashion, it is called an ‘atactic’ polymer.
If the arrangement of side groups is in alternating fashion (trans arrangement), it is called a
‘syndiotactic’ polymer.
4. Classification based on the method of preparation
Addition polymers: The addition polymers are formed by the
repeated addition of monomer molecules possessing double or
triple bonds, e.g., the formation of polyethylene from ethene and
polypropene from propene.
Condensation Polymers: The condensation polymers are formed by repeated condensation reactions
between two different bi-functional or tri-functional monomeric units. In these polymerization
reactions, the elimination of small molecules such as water, alcohol, hydrogen chloride, etc. takes
place. Examples are terylene, nylon-6,6, nylon-6, etc.
Molecular weight of polymers
Number Average, Weight Average Molecular Weight of polymers
Polymers are polydisperse and quite heterogeneous in their molecular weight. In other words,
polymers are mixtures of molecules of different molecular weights. Statistically, they are expressed as
number average molecular weight (Mn), weight average molecular weight (Mw), and viscosity average
molecular weight (Mv).
Number Average Molecular weight (Mn): It is determined by measurement of colligative properties
such as depression in freezing point, elevation of boiling point, osmotic pressure, and lowering of
vapor pressure. It is defined as the total mass of all the molecules in a polymer sample divided by the
total number of molecules present. Thus, the number average molecular weight is given by
Mn = ΣNiMi/ΣNi where Ni is the number of molecules having molecular weight Mi
The number average molecular weight is a good index of physical properties such as the impact of
tensile strength, but not a good index of other properties such as flow.
Weight average molecular weight (Mw): It is obtained by light scattering and ultra-centrifugation
technique, which measures the molecular size. It is given by,
Mw = ΣNiMi2/ΣNiMi
The weight average molecular weight is always greater than number average molecular weight for the
polydisperse system. Moreover, Mn = Mw in the case of monodisperse system (i.e., in which all
molecules have identical molecular weight, eg. acetone, benzene).
Numerical Problem: For a polymer sample containing equal numbers of polymer molecules of
molecular weight 20 kDa, 80 kDa, and 120 kDa, calculate 𝑀 n, 𝑀 w, and PDI.

3 Dr. AN, Dept. of Chemistry, BMS CE (2024-25 – II, for PD & PX)
Glass transition temperature (Tg)
“The glass transition temperature is the temperature at which a polymer abruptly transforms from the
glassy state (hard) to the rubbery state (soft)”.
When an amorphous polymer is heated, it gets converted from a hard brittle state (glassy state) to a
soft flexible state (rubbery state). The temperature at which a polymer transforms from a hard glassy
state to a soft rubbery state is called glass transition temperature.
Significance of Tg
 It is used as a measure for evaluating the flexibility of a polymer and the type of response the
polymeric material would exhibit to
 Tg is very useful in choosing the right processing temperature for fabrication (moulding,
calendaring, and extrusion)
 Tg is very useful in determining the coefficient of thermal expansion, heat resistance, refractive
index, electrical property, etc.
Factors affecting glass transition temperature (Tg)
1. Chain Flexibility: Linear polymer chains have a high degree of freedom for rotation i.e., more
chain flexibility and low Tg. Aromatic or cyclic groups on the backbone of carbon atoms hinder the
freedom of rotation i.e., chain flexibility decreases and causes an increase in Tg. Ex: Tg of
polyethylene is -110 °C whereas that of polybutadiene and polyphenylene oxide is -85 and +83 °C,
respectively arising due to hindered rotation around double and bond and the presence of aromatic
rings.
2. Cross-linking and branching: A small amount of branching will tend to lower Tg and a high
density of branching reduces chain mobility and elevates the Tg. The cross-linking brings the polymer
chain closer, lowers free volume restricts molecular motion, and hence rises Tg.
3. Intermolecular forces: The presence of a large number of polar groups in the molecules leads to
strong intermolecular cohesive forces which restrict the segmental motion. As a result, Tg increases.
Ex: the Tg value of polypropene is -18 °C, whereas that of nylon 6 containing polyamide (polar)
groups is 57 °C.
4. Molecular mass: The higher the molecular mass more the restriction in the molecular freedom.
However, the Tg value of all polymers in general increases with molecular weight up to 20,000,
beyond which the effect is negligible.
5. Presence of plasticizers: The addition of plasticizers reduces the Tg value; for example, the
addition of di-isooctyl phthalate to pvc reduces its Tg from 83 °C to below room temperature.
6. Crystallinity: The higher the crystallinity, larger the Tg value of a polymer. Ex: Polyethylene
polymer has a Tg value of -110 °C because it has less crystallinity (amorphous), whereas nylon 6 has
high crystallinity, and hence its Tg is 57 °C.

4 Dr. AN, Dept. of Chemistry, BMS CE (2024-25 – II, for PD & PX)
7. Effect of side group: The polymers having side groups have high Tg values, whereas the polymers
not having side groups have low Tg values. Ex: Poly(α-methyl styrene) has a higher Tg value (170 °C)
as compared to polystyrene (100 °C).
Relationship between structure and property of a polymer
The structure of a polymer has a profound influence on
some of its properties. The properties such as crystallinity,
tensile strength, elastic nature, and chemical resistance are
largely dependent on the structure of the polymer.
1. Tensile strength: Density, melt viscosity, and tensile
strength are a few important mechanical properties of a
polymer. These are highly influenced by the molecular weight
of polymers. Tensile strength increases with the molecular mass of the polymer up to 20,000. Beyond
that the increase is negligible. Low molecular weight polymers are generally soft and gummy and
strength increases with chain length and molecular weight. Strength also depends upon the slipping
power of chains. For example, chains of polyethylene can slip whereas PVC can do so with great
difficulty because C-Cl polar bond can establish intermolecular forces of attraction. Therefore, PVC is
stronger and tougher than polyethylene. If the chains are cross-linked through covalent bonds the
movement of chains is totally restricted. Such polymers will have very high strength like bakelite. The
presence of polar groups such as –OH and –C=O, greatly increases of intermolecular forces of
attraction. The high strength of nylons and polyesters can be attributed to this.
2. Crystallinity: The degree of crystallinity of a polymer depends on its structure and stereo
regularity. The crystallinity regions of polymer are formed when the individual chains are linear, have
no bulky groups, and are closely arranged parallel to each other. The adjacent chains of polymers are
held together by strong cohesive forces. Such a close packing of chains leads to a high degree of
crystallinity and gives high tensile strength, impact resistance, sharper melting point, lesser solubility
and greater chemical resistance, high density, and Tg values. Ex: - HDPE, isotactic and syndiotactic
polypropylene, PVC, etc.
Configuration of the polymer: Isotactic Polymers are more crystalline than atactic polymers. Ex:
Isotactic polyvinyl chloride is more crystalline than atactic polyvinyl chloride (random arrangements
of groups).
It also depends on polar groups and hydrogen bonding for those polymers having polar groups and
hydrogen bonding have a high degree of crystallinity.
3. Chemical. Resistance: Polymers should have more resistance to chemical attacks and should not
become soft, swell, or lose their strength. The chemical resistivity of a polymer depends on mainly.

5 Dr. AN, Dept. of Chemistry, BMS CE (2024-25 – II, for PD & PX)
a. Presence of polar and non-polar groups in the polymer chain. Polymers that have polar groups such
as –OH, –COOH, are less resistant to chemical attack. But non-polar groups such as –CH 3, –C6H5,
etc., are not usually attacked by chemicals.
Ex: PVC, ABS, polystyrene, etc., have high resistance to chemicals.
b. Degree of crystallinity: Chemical resistance increases with an increase in degree of crystallinity
because crystalline regions make the penetration of chemicals or solvents more difficult. The higher
the degree of crystallinity higher the chemical resistance.
Resin and Plastics
Plastics - These are organic materials of high molecular weight (polymers), which can be molded into
any desired form, when subjected to heat, and pressure in the presence of a catalyst. Plastics possess
unique properties – lightness in weight, corrosion resistance, thermal and electrical insulation, high
resistance to abrasion, chemical attack, high refractive index, water repellant, decorative finish, etc.
They are very important engineering materials used for making electrical goods, furniture, floor and
wall linings, plugs, switches, holders, propeller shafts, rolling mills, refrigeration, storage, lenses,
fibers, etc.
Resin is a solid, liquid, or semisolid organic polymer used as the basis for plastics, adhesives, and
varnishes. Resins are basic binding material that forms a main part of the plastic and which actually
has undergone polymerization reactions during the preparation or molding of plastic. It is also a
binder, which holds the different constituents together. It is the resin that undergoes chemical reactions
like condensation, cross-linking, etc. during molding. They contribute mainly to the properties of the
final product. Examples are thermosetting resins of low molecular weight which are fusible and
moldable in the presence of catalysts.
Ex: PVC, phenol formaldehyde resin, nylons, polyester, etc.
Preparation and applications of polymethylmethacrylate (PMMA) (Plexi glass)

Plexi glass is the trade name of polymethylmethacrylate. The monomers used for the preparation
of plexi glass are methyl methacrylate. PMMA is prepared by emulsion polymerization method at -70
°C in the presence of catalytic H2O2 or acetyl peroxide as initiator.
Properties
i. Plexi glass is a white transparent thermoplastic
ii. High optical clarity
Applications

6 Dr. AN, Dept. of Chemistry, BMS CE (2024-25 – II, for PD & PX)
i. It is used in the preparation of aircraft windows
ii. Attractive sign boards
iii. Manufacturing of transparent molded articles and tubes
iv. Lenses for automobiles, artificial eyes, etc.
Preparation and applications of Urea-Formaldehyde Resins (UF Resin)
Synthesis: It is prepared by the condensation of urea with formaldehyde in the presence of a base in a
stainless-steel reactor at 50 °C. The initial products mono, dimethylol urea are compounded by the
addition of filler, plasticizer, pigment, or catalyst followed by curing by applying heat and pressure to
provide long -C-N-C-N chain polymer. This is called urea-formaldehyde resin and is a cross-linked
polymer.
Properties: It gives clear, water-white products of good tensile strength, good electrical insulation,
good chemical resistance, greater hardness, and good abrasion resistance.
Applications: It is employed for bonding grinding wheels, as cation-exchange resins, binder for glass
fibre, rock, wool, plywood, to provide electrical insulation, etc.
O O HCHO
HCHO HN CH2OH
H2N NH2 H2N NH O
base
CH2OH HN CH2 OH
Urea
monomethylol urea dimethylol urea
O O O
O O
H2 H H2N N N N N N OH
H2 N N C OH + N N CH2OH -H2O H H H H H
H H H
n
monomethylol urea compounding followed by
HCHO curing, heat, preassure
-nH2O
O
H2 H
N C N C N
n
Urea-Formaldehyde Resin
H H2
N C N C N
O
n

Elastomers
They are high molecular weight polymers possessing elastic properties. i.e., they can undergo
deformation under stress (to an extent 5-10 times of original length) but regain their original shape
when the stress is released. This property is called elasticity and it is due to the coiled nature of chains
in them. Natural rubber is an example of an elastomer. But natural rubber has certain drawbacks such
as being degraded easily by sunlight and air, absorbing moisture, having low tensile strength, and
becoming hard and brittle at low temperatures.

7 Dr. AN, Dept. of Chemistry, BMS CE (2024-25 – II, for PD & PX)
Advantages of synthetic rubber - (a) resistance to heat and light (b) water repellent and solvent
resistance (c) high chemical resistance towards alkali/acid (d) high temperature stability (e) high
abrasion resistance.
Preparation and applications of butyl rubber
Synthesis: Butyl rubber is synthesized by reacting isobutylene with up to 5% of isoprene monomer
using methyl chloride (CH3Cl) as solvent using anhydrous aluminium chloride (AlCl 3) as catalyst at -
95 °C. The product was vulcanized and dried by mixing with antioxidants.

Properties: It is less sensitive to oxidative aging. It has very low gas permeability and shows good
solvent resistance. It has excellent resistance to heat, abrasion, aging, chemicals, and polar solvents
like alcohol and acetone. It has good electrical insulation properties.
Applications: (a) inner tube for tires, automobile parts, hoses, tank linings (b) insulating materials for
high voltage transmission lines and cables.
Nitrile Rubber (Buna-N or Europrene)
Synthesis: Nitrile rubber is synthesized by emulsion polymerization of butadiene and acrylonitrile
monomers in a steel vessel at 30-40 °C using water as a solvent in the presence of H 2O2 as a free
radical initiator. The resulting polymer latex was coagulated followed by vulcanization to provide
nitrile rubber.

Properties: Nitrile rubber co-polymer has high tensile strength, excellent resistance to heat, sunlight,
oils, fats, organic solvents, and dilute acids but it is less resistant to alkalies due to the presence of base
labile -CN group. Lower acrylonitrile composition in the nitrile rubber led to a decrease in glass
transition temperature (Tg) and shows greater resistance to solvents upon increasing nitrile
composition. This rubber can withstand a temperature of -40 °C to 100 °C.
Applications: (a) Nuclear, medical, and aeronautical industry applications since it can withstand low
and high temperatures (b) Used as a sealant, expanded foam, floor mats, non-latex gloves, automotive
transmission belts, gaskets, oil seals (c) as the pigment binder, fuel, and oil handling hoses.

8 Dr. AN, Dept. of Chemistry, BMS CE (2024-25 – II, for PD & PX)
Biodegradable polymers
Biodegradable polymers contain polymer chains that are hydrolytically or enzymatically cleaved,
resulting in soluble degradation products. Biodegradability is particularly desired in biomedical
applications, in which degradation of the polymer ensures clearance from the body and eliminates the
need for retrieval or explant. Biodegradable polymers have applications in,
Controlled/sustained release drug delivery approaches
Tissue engineering scaffolds
Temporary prosthetic implants
Polyglycolic acid (Polyglycolide) (PGA)
Polyglycolic acid is obtained through ring-opening polymerization of glycolide, the cyclic diester of
glycolic acid. Ring-opening polymerization of glycolide can be catalyzed using aluminum
isopropoxide. In the presence of a catalyst glycolide, is heated to a temperature of 195 °C to produce
polyglycolic acid. The other method is direct polymerization of glycolic acid to produce PGA.
Generally, direct polymerization of glycolic acid offers a polymer having low molecular weight.

PGA is characterized by hydrolytic instability owing to the presence of the ester linkage in its
backbone. In the degradation process first water diffuses into the amorphous (non-crystalline) regions
of the polymer matrix, cleaving the ester bonds; the second step starts after the amorphous regions
have been eroded, leaving the crystalline portion of the polymer susceptible to hydrolytic attack. Upon
collapse of the crystalline regions, the polymer chain dissolves.
When exposed to physiological conditions, PGA is degraded by random hydrolysis, and apparently, it
is also broken down by certain enzymes, especially those with esterase activity. The degradation
product, glycolic acid, is nontoxic, after which it is excreted as water and carbon dioxide. A part of the
glycolic acid is also excreted by urine.

9 Dr. AN, Dept. of Chemistry, BMS CE (2024-25 – II, for PD & PX)
Polymer composites
A composite material is a hybrid material formed by the combination of two or more dissimilar
materials to produce a new material, having the advantageous properties of the different components.
A composite material is better suited for a particular application than all of the original materials
alone. Modern technologies require materials with unusual combinations of properties that cannot be
met by conventional polymeric materials, alloys, ceramics, and cement. These materials can be
combined in composite material to produce unique characteristics such as stiffness, toughness, and
high-temperature resistance. These types of materials find use, particularly in aerospace, underwater,
and transportation applications. The composite materials comprise two phases ‘matrix’, which is the
continuous phase, and the ‘dispersed phase’ or the reinforcing material. The most common example of
composite material is fibre-glass reinforced plastic (FRP). The plastic acts as the matrix and fibre
glass is the dispersed phase. Plastic alone is relatively weak and has a low elastic modulus, that is, it
bends and stretches easily. The glass fibres provide it strength and stiffness, and their modulus of
elasticity may be 50 times greater than that of plastic alone. Glass fibres take most of the load when
the composite is stressed.
Carbon Fiber is a polymer and is sometimes known as graphite fiber. It is a very strong material
that is also very lightweight. Carbon fiber is five times stronger than steel and twice as stiff. Though
carbon fiber is stronger and stiffer than steel, it is lighter than steel; making it the ideal manufacturing
material for many parts. These are just a few reasons why carbon fiber is favored by engineers and
designers for manufacturing.
Carbon fiber is most notably used to reinforce composite materials, particularly the class of
materials known as carbon fiber-reinforced polymers. The fiber finds use in the filtration of high-
temperature gases, as an electrode with high surface area and impeccable corrosion resistance.
Molding a thin layer of carbon fibers significantly improves the fire resistance of polymers or
thermoset composites because a dense, compact layer of carbon fibers efficiently reflects heat.
The increasing use of carbon fiber composites is displacing aluminum from aerospace applications
in favor of other metals because of galvanic corrosion issues.
Carbon fiber can be used as an additive to asphalt to make electrically conductive asphalt concrete.
Using this composite material in the transportation infrastructure, especially for airport pavement,
decreases some winter maintenance problems that lead to flight cancellations or delays due to the
presence of ice and snow. Passing current through the composite material 3D network of carbon fibers
dissipates thermal energy that increases the surface temperature of the asphalt, which is able to melt
ice and snow above it.

10 Dr. AN, Dept. of Chemistry, BMS CE (2024-25 – II, for PD & PX)
Kevlar Fiber
It is an aromatic polyamide, poly(p-phenyleneterephthalamide). It is prepared by the polycondensation
of aromatic dichloride and aromatic diamines.

Properties
Kevlar has extraordinary mechanical properties, high elastic modulus, and high tensile strength.
Kevlar is known for its ability to be spun into fibres that have five times the tensile strength of steel
and 10 times that of Al on a weight-to-weight basis. The high tensile strength is due to extensive
hydrogen bonding between the adjacent polymeric chains. It has extreme chemical inertness, high heat
stability, and flexibility. It is also extremely resistant, to fire.
Uses
It is used in the fabrication of protective wear including bullet-proof vests. It is extensively used in
aerospace and aircraft industries, boat hulls, drum heads, sports equipment, car parts (such as tires,
brakes, clutch linings), helmets, brake pads, ropes, cables, etc. Kevlar is generally used as a composite
material with carbon or glass fibers.
Conducting polymers
“An organic polymer with highly delocalized pi-electron system, having electrical conductance of
the order of a conductor is called a conducting polymer”. Heeger, Macdiarmid, and Shirakawa, in
1977, demonstrated for the first time that the electrical conductivity of polyacetylene can be increased
to 13 folds by doping with electron acceptors or donors. Tremendous applications would exist as they
are flexible, ease of fabrication, stability, ease of processability, etc.
Key structural feature of conducting polymer - linear structure with alternate single and double
bonds, i.e., extensive pi conjugation in the backbone.

11 Dr. AN, Dept. of Chemistry, BMS CE (2024-25 – II, for PD & PX)
The conducting polymers are synthesized by doping, in which charged species are introduced into
organic polymers having pi-backbone. The main doping reactions are (a) oxidative doping (p-doping)
(b) reductive doping (n-doping) and (c) protonic acid doping. The electrical conductivity of doped
polyacetylene (105 sm-1) is remarkable to Teflon (10-8 sm-1) but is lower than copper (108 sm-1).
Examples: some of the conducting polymers are shown below,

Polyacetylene

H H
N N Polypyrrole
N N N
H H H

Polyphenylene

NH NH NH NH Polyaniline

Applications of conducting polymers

They are used as electrode material in capacitors, ion exchange devices, light emitting diodes,
electrochromic display windows, bio-sensors, humidity sensors, radiation sensors, conductive tracks
on PCB, etc.
Synthesis and conducting mechanism of polyacetylene
The poly(acetylene) (PA) is prepared by passing acetylene gas over the Zeigler Natta catalyst. Zeigler-
Natta catalyst is the coordination complex of tetra butoxy titanium, (Ti(OBu)4), an organo-metallic
compound, and triethyl aluminum, (Et3Al).

The reaction forms copper colored cis-poly(acetylene), having conductivity in the range of 10-8 - 10-7
S/cm, at low temperatures (-78 oC). At higher temperatures (150 oC), more stable silver-colored trans-
poly(acetylene), having conductivity in the range of 10-3 -10-2 S/cm is formed. Cis-poly(acetylene) can
be converted to trans-poly(acetylene) by heating it at 150 oC for a few minutes.

12 Dr. AN, Dept. of Chemistry, BMS CE (2024-25 – II, for PD & PX)
Applications: Doped Polyacetylene offers good electrical conductivity, hence can be used as
electrode material in light weight rechargeable batteries. I3- dopped acetylene can also be used in
biosensors.

END
Acknowledgments: Dr. GM, Dr. KLN (Dept. of Chemistry, BMSCE)

13 Dr. AN, Dept. of Chemistry, BMS CE (2024-25 – II, for PD & PX)