Chemistry of Polymers

• Overview of polymers
• Types of polymerization
• Tacticity
• Molecular weight determination
• Industrial applications of polymers in
fiber, paints, and coatings
• Conducting polymers
• Biodegradable Polymers
• Polymers in automotive industry.
Serendipity in 1839

Charles Goodyear

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 1907

Dr. Leo Baekeland

Bakelite- the first synthetic plastic.

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 Bakelite

Radios, telephones and electrical insulators were

made of Bakelite in the past due to its insulating and
heat-resistant properties.
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 1917

M.Polanyi

Used X-ray crystallography to discover the chemical

structure of cellulose-a long chain molecule. 5
 POLYMERS

Poly + mer
many repeat unit (building blocks)
Polymers are macromolecules formed by small units i.e. monomers.

Types of polymers

Polymers

Natural Synthetic

Occur in nature Fibres synthetic rubbers Plastics

ex. wool, cellulose, protein, Nylon, terrylene Neoprene
Rubber, Starch, nucleic acids

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Synthetic Polymer: Nylon

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Natural Polymer: Cotton

Long Strands of Cellulose

+ Hydrogen Bonds

Cellulose is the most common organic material on earth!

It is also a primary constituent of wood and paper.
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Polymers in Starch
Biology
DNA

Sugar Proteins

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• Chains with only one type of monomer: HOMOPOLYMERS
• Chains with a mixture of two or more monomers: COPOLYMER

Copolymer configurations

Produced by special techniques to give

certain specific properties to the product

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 Polymerization Reactions
• The chemical reaction in which high molecular mass molecules are formed
from monomers is known as polymerization.

There are two basic types of polymerization –

• Chain-reaction (or addition) and
• Step-reaction (or condensation) polymerization.

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 Addition (Chain) Polymerization

– Initiation

– Propagation

– Termination

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Some Common Addition Polymers

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Molecular Structure
of Polymers
 Linear
 High Density Polyethylene (HDPE), PVC, Nylon,
Cotton
 Branched
 Low Density
Polyethylene (LDPE)
 Cross-linked
 Rubber
 Network
 Kevlar, Epoxy
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Chain Length: 1000 - 2000

Low-Density Polyethylene (LDPE)

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Chain Length: 4,000 – 5,000

PVC – (polyvinyl chloride)

More Polar  Stronger Bonding

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Chain Length: 10,000 – 100,000

High-Density Polyethylene (HDPE)

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Chain Length: 2-6 million

Ultra-high-molecular-weight
polyethylene (UHMWPE)
Joint
Replacement

Helmet

Gears
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Rubber Tree

 Sap:
 Sticky
 Viscous
 Gooey
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Vulcanization
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Cross linking adds

tensile strength
 Condensation (Step) Polymerization

• Involve two different types of di-functional monomers or end groups that

react with one another, forming a chain and also produces a small
molecular by-product (water, HCl, etc.)

• As the chain grows, the short chain molecules are called oligomers.
• This reaction process can, theoretically, continue until no further monomers
and reactive end groups are available.
• The process, however, is relatively slow and can take up to several hours or
days. 22
 Thermoplastics and Thermosetting
• The response of a polymer to mechanical forces at elevated
temperature is related to its dominant molecular structure.
• One classification of polymers is according to its behavior with
rising temperature. Thermoplastics and Thermosetting are the 2
categories.
• A thermoplastic is a polymer that turns to a liquid when heated
and freezes to a very glassy state when cooled sufficiently.
• Most thermoplastics are high-molecular-weight polymers whose
chains associate through weak Van der Waals forces
(polyethylene); stronger dipole-dipole interactions and hydrogen
bonding (nylon).
• More examples: Polystyrene and cellulose acetate

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 Thermoplastics and Thermosets
• Thermoplastic polymers differ from thermosetting
polymers (Bakelite, vulcanized rubber) since
thermoplastics can be remelted and remolded.
• Thermosetting plastics when heated, will
chemically decompose, so they can not be
recycled. Yet, once a thermoset is cured it tends to
be stronger than a thermoplastic.
• Typically, linear polymers with minor branched
structures (and flexible chains) are thermoplastics.
The networked structures are thermosets.
• Phenol-formaldehyde and urea formaldehyde
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Polymer Microstructure
Polyolefins with side chains have stereocenters on every other carbon

CH3
n
CH3 CH3 CH3 CH3 CH3 CH3 CH3

With so many stereocenters, the stereochemistry can be complex. There are

three main stereochemical classifications for polymers.

Atactic: random orientation

Isotactic: All stereocenters have same orientation

Syndiotactic: Alternating stereochemistry

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Effect of Tacticity

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 Why is this important?
• Tacticity affects the physical properties
– Atactic polymers will generally be amorphous, soft, flexible
materials
– Isotactic and syndiotactic polymers will be more crystalline,
thus harder and less flexible
• Polypropylene (PP) is a good example
– Atactic PP is a low melting, soft material
– Isoatactic PP is high melting (176º), crystalline, tough
material that is industrially useful
– Syndiotactic PP has similar properties, It is harder to
synthesize

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 Molecular Weight Determination

• Almost all the properties of polymer changes with degree of

polymerization, and hence its applications.

• Polymer – complex mixture of molecules of different molecular wts.

- Polydisperse and heterogenous in composition

• Mol. wt of polymer – Average of mol. wts of constituent molecules

• Different types of average mol. wts can be obtained

• Number Average - Weight Average - Viscosity average

Mn Mw Mv

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• Mn = [N1M1 + N2M2 + N3M3 + -----]
= S NiMi/ S Ni
N1 + N2 + N3 + ----
Where N1, N2, N3 – No. of molecules
M1, M2, N3 – Mol. wts
• Mw = [N1M12 + N2M22 + N3M32 + -----]
= S NiMi2/ S NiMi
N1M1 + N2M2 + N3M3 +--

• Mv = S NiMi(1+a) 1/a a - Constant

S NiMi
If a = 1 Mv = Mw
But, a ranges from 0.5 – 0.9, so, Mv < Mw
For a polydisperse system For monodisperse system
Mw > Mv > Mn Mw = Mn
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 Degree of Polymerization, DP

DP = average number of repeat units per chain

Mn
DP =
m
where m = repeat unit molecular weight

Ex. for PVC: if Mn = 21150 g/mol

m = 2(carbon) + 3(hydrogen) + 1(Chlorine)
= 2(12.011) + 3(1.008) + 1(35.45)
= 62.496 g/mol
DP = 21,150 / 62.496 = 338.42
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 Variation of mech. Properties with DP

• Tensile strength and impact resistance increases with increase in degree of

polymerization upto a point after which slow increase is there
• Melt flow viscosity initially increases slowly then rapidly after the polymer
has attained a certain degree of polymerization
• RI, colour, density, and electrical properties are independent of the molecular
weight of polymer

Melt
Tensile strength viscosity
property
Impact res.

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Deg. of polymerization
 Threshold Molecular Weight

• Lower molecular weight polymer – Brittle and less mechanical strength.

• Very high mol. wt. Polymer – Tough and intractable cannot be easily handled.

• Polymerization process should be controlled after certain stage depending

upon the application.

• Threshold molecular weight is the minimum molecular weight that a polymer

must attain to develop the properties needed for a particular application

• Physical properties of polymer such as tensile strength and impact resistance

are related to mol. wt and mol. wt distribution of the polymer

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Practice Problems

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Take home message
• PDI
• Tacticity: stereochemistry
• Thermoset, thermoplastics
• LDPE/HDPE
• colligative
• light scattering
• Degree of Polymerisation
• Impact Resistance, Tensile Strength
•

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 Biodegradable Polymers
Degradable plastics in which degradation results from action of
naturally occurring microorganism such as bacteria, fungi, algae.
Classification of Biodegradable Polymers:
1. Naturally Biodegradable Polymers
2. Synthetic biodegradable Polymers
Natural biodegradable polymer occur in nature by living
organisms
e.g. Starch, protein, cellulose etc. degraded by hydrolytic
enzymes of microorganisms

Synthetic Biodegradable synthesised by mankind

e.g. Aliphatic polyesters containing polylactic acid hydrolyzed
by lactate.
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Examples of Biodegradable Polymers
Polyhydroxyalkanoates (PHA)
Polylactic acids (PLA)

Applications of biodegradable Polymers:

Food Packing
Single serve cups or other disposable food
service items
Medical : as bone plates and surgical surtures

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 Conducting Polymers
Organic polymers with highly delocalized pi-electron system
having electrical conductance of the order of conductors are called
conducting polymers.
Polyphenylene

Polythiophene
S S S

S S

Polyphenyl vinylene

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Conjugated organic polymers in their pure state are either insulator or
semiconductors.
The p-e-s are normally localized and donot take part in conductivity
The electrons delocalize on doping and conduct electricity.
Dopant can be oxidizing or reducing agent and protonic acid.
Most organic conductors are doped oxidatively to give p-type materials

Applications of Conducting Polymers

Used as electrode materials for rechargeable batteries
Used in light emitting diodes and display devices
Used as resistors for storage devices

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 Inorganic polymers
Inorganic polymers are polymers with a skeletal structure that does not include carbon
atoms in the backbone. Inorganic polymers offer some properties not found in organic
materials including low temperature flexibility, electrical conductivity, and nonflammability.
Inorganic polymers focus on 1-dimensional polymers, not heavily crosslinked materials such
as silicate minerals.
Homochain polymers
Homochain polymers have only one kind of atom in the main chain. One member is
polymeric sulfur, which forms reversibly upon melting any of the cyclic allotropes, such as S8.
Organic polysulfides and polysulfanes feature short chains of sulfur atoms.
Heterochain polymers
Si-based
Heterochain polymers have more than one type of atom in the main chain. Typically two
types of atoms alternate along the main chain. Of great commercial interest are the
polysiloxanes where the main chain features Si and O centers, -Si-O-Si-O-.
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1.8 Industrial Polymers

The world’s consumption of synthetic polymers

: 150 million metric tons per year.

1) Plastics : 56%
2) Fibers : 18%
3) Synthetic rubber : 11%
4) Coating and Adhesives : 15%

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 Fibers

Defined as flexible, macroscopically homogeneous body having a high

length to width ratio and small cross section.
Types of Fibres:
1. Naturally occurring Fibres:
 Plant origin based on cellulose: Cotton, Jute, Ramie
 Animal origin based proteins: Silk, wool
 Mineral origin: Asbestos
2. Regenerated Fibres (Semisynthetic):
 Rayon Containing regenerated cellulose
 Acetate containing partially acetylated cellulose
 Azlon Containing regenerated protein
3. Synthetic fibres (Synthetic organic polymer)
 Acrylic (polyacrylonitrile)
 Aramid (Aromatic Polyamide)
 Nylon (aliphatic polyamide)
 Polyester (polyester of aromatic dicarboxylic acid and dihydric
alcohol)
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 Vinal (Polyvinyl Chloride)
Examples of Synthetic and semi-synthetic fibres
(1) Polyethylene terephthalate (Polyester)
O O
H2
C
HO 2 OH
HO OH

O O

* O O *
2
O O n
2

Applications
 Used for making clear bottles for foods and
beverages
 Being an insulator used as moulds for electric
appliances
 To make films for shrink packaging 43
Acrylic Fibres (Polyacrylonitriles)

Applications
 Substitute of wool (artificial wool).
 Fibres obtained from copolymerization of methyl acrylate and
methylmethacrylate are used to make knitted clothing like socks
sweaters etc.
 Copolymers such as styrene-acrylonitrile and styrene-
acrylonitrile-butadiene used as plastics 44
1.8.4 Coating and Adhesives

1) Coating :

Lacquer, Vanishes, Paint (Oil or Latex), Latex

2) Adhesives :

Solvent based, Hot melt, Pressure sensitive, etc.

Acrylate, Epoxy, Urethane, Cyanoacrylate

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 Polymer Applications in Automobiles
• Plastics vs. Metals
- Instrument Panels
- Engine
- Windows
- Tires
- Body Panels

Why Plastic???
• Compete with other materials based on:
• Weight savings
• Design flexibility
• Parts consolidation
• Ease of fabrication
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 Car Part Polymer
Trim Panels (3) Polypropylene (PP)
Impact Absorber Thermoplastic Olefin (TPO)
Radio Housing ABS/Polycarbonate(PC)
Door Outer Panel ABS/Polycarbonate(PC)
Handle Polypropylene (PP)
Fog Light Cover Thermoplastic Elastomeric
Olefin (TEO)
Tire Elastomers

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Polymer material used for Automotive industry

(i) Polycarbonate (PC)

Polycarbonates are often used for the application in automotive industry.
main application in automobiles is for the manufacture of various parts of
light assemblies, such as lights and lenses of the front and rear lights.
It features the following properties:
- resistant to high temperatures (up to 148°C),
High-temperature polycarbonate (PC-HT) is resistant to temperatures (from
160-220oC);
- transparent with possibility of being painted into any nuance;
- Good electric and insulation properties
- high dimensional stability, precision and good properties of toughness;
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(ii) Acrylonitrile/butadiene/styrene (ABS)
Primarily used for the manufacture of housings, covers and linings,
featuring the following properties:
- very good properties of toughness, strength and rigidity;
- they are opaque, attain high surface polish i.e. have well polished
surface;
- good chemical resistance and resistance to temperature of 80-
105°C;

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(iii) Thermoplastic alloy
Most commonly used alloy for automobile parts are:
(a) polycarbonate+acrylonitrile/butadiene/styrene (PC+ABS)
(b) acrylonitrile/butadiene/styrene+polyamide (ABS + PA).
The alloys allow combining of mechanical, thermal and rheological properties of
materials.
Alloy (PC+ ABS) is used for the internal and external decorative and small bodywork
parts,
Features the following properties:
- it is opaque, has high surface polish;
- resistance to temperature between ABS and PC;
- high dimension stability and reaches high precision in the production of small parts;
- slight tendency to distortion and humidity absorption;
- features good electric insulation properties;
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