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POLYMERIC MATERIALS

POLYMERS

A large class of materials consisting of many small

molecules (called monomers) that can be linked
together to form long chains, thus they are known
as macromolecules

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• Polymer = many mers (repeating units)

mer mer mer

H H H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C
H H H H H H H Cl H Cl H Cl H CH3 H CH3 H CH3
Polyethylene (PE) Polyvinyl chloride (PVC) Polypropylene (PP)

Carbon chain backbone

Types of Polymerization
 Addition/Chain growth polymerization: Small molecules
covalently bond to form long chains which in turn bond to
form polymers.
 Example: Ethylene

H H H H
Heat
n C C C C
Pressure
Catalyst
H H H H n
n=degree of
Polymerization (DP)
Molecular mass of polymer(g/mol)
DP = Mass of a mer (g/mol)

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Chain Polymerization - Steps

 Initiation:
 A Radical is
needed
 Example H2O2
In General

• One of free radicals react with ethylene molecule

to form new longer chain free radical.

Chain Polymerization – Steps

(cont..)
 Propagation: Process of extending polymer chain by
addition of monomers.

R CH2 CH2 + CH2 CH2 R CH2 CH2 CH2 CH2

 Termination:-
 Combining of two chains
 Disproportionation

R(CH2 CH2)m + R’(CH2 CH2)n R(CH2 CH2)m R (CH2 CH2)n R’

Coupling of two chains

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 Combination
It occurs when the polymer's growth is
stopped by free electrons from two growing
chains that join and form a single chain. The
following diagram depicts combination, with
the symbol (R) representing the rest of the
chain.

 Disproportionation
It halts the propagation reaction when a free
radical strips a hydrogen atom from an
active chain. A carbon-carbon double bond
takes the place of the missing hydrogen.

Disproportionation can also occur when the

radical reacts with an impurity. This is why it is
so important that polymerization be carried out
under very clean conditions.

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Some Common Addition Polymers

 Stepwise/Condensation
Polymerization:
Monomers chemically react with each
other to produce linear polymers
and a small molecule of byproduct.

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Some Condensation Polymers

Natural Polymers
Monomer Polymer

Isoprene Polyisoprene:
Natural rubber n

H OH H OH
HO H HO
HO O
HO OH HO OH
H OH Poly(ß-D-glycoside): H OH
H H cellulose H H n

ß-D-glucose
O O O O
H H
H3N H3N N N OH
O Polyamino acid:
protein R1 Rn+1 n Rn+2
R
Amino Acid
O O
DNA
O P O Base O P O
O Base
O O O
oligonucleic acid
OH DNA
O
Nucleotide DNA
Base = C, G, T, A

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Common Polyolefins
Monomer Polymer
CH3
H3C
Polyethylene n
Ethylene Repeat unit

CH3
CH3 n
Polypropylene CH3 CH3 CH3 CH3 CH3 CH3 CH3
Propylene

CH3
Ph n
Polystyrene Ph Ph Ph Ph Ph Ph Ph
Styrene

CH3
Cl n
Poly(vinyl chloride) Cl Cl Cl Cl Cl Cl Cl
Vinyl Chloride
F2 F2 F2 F2 F2 F2
F2C CF2 C C C C C C CF3
F3C C C C C C C
F2 F2 F2 nF F2 F2
Tetrafluoroethylene Poly(tetrafluoroethylene): Teflon 2

Polyesters, Amides, and Urethanes

Monomer Polymer
O O
H2 H2
HO2C CO2H OH HO O C C O H
HO
Ethylene Poly(ethylene terephthalate n
Terephthalic
acid glycol Ester

O O O O
H
HO 4
OH H2N 4
NH2 HO N N
4
4
Adipic Acid 1,6-Diaminohexane Nylon 6,6 H H n
Amide
O O
H H
HO2C CO2H H2N NH2 HO N N H
Kevlar n
Terephthalic 1,4-Diamino
acid benzene

H2
OCN C NCO OH
HO
Ethylene Spandex
4,4-diisocyantophenylmethane
glycol
O O
H H2 H H2 H2
HO N C N O C C O H Urethane linkage
n

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Merits of Polymeric Materials

 Good electrical and thermal insulation

 Light weight
 Good strength/weight ratio, toughness, durability
 Optical transperancy
 Easy workability (casting, moulding, drilling, etc.)
 Chemical/Moisture Resistant
 Do not rust/corrode
 Resistant to microbes
 Non toxic
 Good weatherability
 Practically maintenance free
 Reusable / Recyclable

Demerits of Polymeric Materials

 Poor ductility
 Softness
 Brittleness
 Flammability
 Deformation under load
 Low heat resistance
 UV light sensitivity
 Embrittlement at low temperature

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Molecular structure
The physical characteristics of polymer material depend not only
on molecular weight and shape, but also on molecular structure:
1 Linear polymers: van der Waals bonding between chains.
Examples: polyethylene, nylon.

2 Branched polymers: Chain packing efficiency is reduced

compared to linear polymers - lower density (PVC, PS)

3 Cross-linked polymers: Chains are connected by covalent bonds.

Often achieved by adding atoms or molecules that form covalent
links between chains. Many rubbers have this structure.

4 Network polymers: 3D networks made from trifunctional mers.

Examples: epoxies, phenol-formaldehyde

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• Covalent chain configurations and strength:

secondary
bonding

Linear Branched Cross-Linked Network

Direction of increasing strength

Structures of Polymers
 Copolymers
 Idea – polymer that contains more than one
mer unit
 Why? If polymer A has interesting properties,
and polymer B has (different) interesting
properties, making a “mixture” of polymer
should lead to a superior polymer

“Random” copolymer

“Alternating” copolymer – ABABABA…

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“Block” copolymers.
Domains of “pure” mers

“Graft” copolymers. One

mer forms backbone,
another mer is attached to
backbone and is a side
chain (it is “grafted” to the
other polymer)

Copolymers
two or more monomers
polymerized together random
 random – A and B
randomly positioned
along chain
 alternating – A and B
alternate in polymer alternating
chain
 block – large blocks of block
A units alternate with
large blocks of B units
 graft – chains of B
units grafted onto A
backbone
graft
A– B– 22

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MOLECULAR WEIGHT & CRYSTALLINITY

• Molecular weight, Mw: Depends on chain length

smaller Mw larger Mw

• Tensile strength (TS):

--often increases with Mw.

•Longer chains are entangled (anchored) better.

Longer chains make stronger polymers

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• % Crystallinity: % of material that is crystalline.

-- TS often increases with % crystallinity.

crystalline
region

amorphous
region

More crystallinity: higher density, more strength, higher

resistance to dissolution and softening by heating

Polymer Crystallinity

Atomic arrangement in
polymer crystals is
more complex than in
metals or ceramics
Unit cells are typically
large and complex

Polyethylene

Polymer molecules are often partially

crystalline (semi-crystalline), with
crystalline regions dispersed within
amorphous material.

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The degree of
polymerization has a
dramatic effect on the
mechanical properties of a
polymer. As chain length
increases, mechanical
properties such as ductility,
tensile strength, and
hardness rise sharply and
eventually level off.

Most of the practically useful polymers have a DP

between 200 to 2000, corresponding to a molecular
weight range from 20,000 to 200,000.

Degree of crystallinity is determined by:

 Rate of cooling during solidification: time is necessary for

chains to move and align into a crystal structure

 Mer complexity: crystallization less likely in complex

structures; simple polymers, such as polyethylene, crystallize
relatively easily

 Chain configuration: linear polymers can crystallize, branches

inhibit crystallization, network polymers almost completely
amorphous, cross-linked polymers can be crystalline or
amorphous

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 Isomerism: isotactic, syndiotactic polymers can crystallize -

geometrical regularity allows chains to fit together, atactic
difficult to crystallize

Isotactic Syndiotactic

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 Copolymerism: crystallize if mer arrangements are

more regular - alternating, block can crystallize more
easily as compared to random and graft

CLASSIFICATION

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THERMOPLASTICS vs. THERMOSETS

• Thermoplastics • Thermosets
--long-chain linear --large cross linking
-- soft, weak, ductile --hard, strong but more brittle
--soften w/heating --do NOT soften w/heating
-- Addition -- Condensation polymerization
polymerization -- Due to cross links, insoluble in
-- soluble in some almost all organic solvents
organic solvents --phenol formaldehyde, epoxies,
-- polyethylene urethanes, urea formaldehyde
polypropylene
polycarbonate
polystyrene

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•80% of the plastics produced are thermoplastics.

•Of these Polyethylene, Polypropylene, Polystyrene and

Polyvinylchoride (PVC) are the most commonly used (70%).

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Classification of Thermoplastics

SMA-Styrene Maleic Anhydride; ASA-Acrylonitrile Styrene Acrylate; PPO-Poly

p-phenylene oxide; POM-Poly oxy methylene; PPS-Poly phenylene sulfide;
PVDC-Poly vinylidene chloride; PVDF-Poly vinylidene fluoride

Commodity plastics

 polyethylene, polypropylene, polystyrene,

polyvinyl chloride, etc.

 Such polymers are used in large quantities

at relatively low costs

 Major applications like tubes, films, profiles,

containers, bottles, sheets, tyres, etc.

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Engineering plastics
 ABS, polyamides, polyesters, polyacetals,
polymethyl methacrylates, etc.

 Such polymers are used for special

requirements at an intermediate cost level
often for very small parts (clips, valves,
special machine parts, etc.)

Speciality polymers
 polyimide, polyphenylene sulfide,
polyethersulfone, polytetrafluoroethylene,
polyetherketone, etc.

 Such low volume, high priced materials are

used to meet extreme requirements like
high temperature, weather or solvent
resistance, special wear or optical
properties, extreme purity for critical
medical applications, etc.

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