Lecture 1

Introduction to Polymers
Chapter 5

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 Objectives

• Polymer terminology
• Difference between natural and synthetic polymers
• Chemical structures of common polymers
• Polymer classification
• Architecture
• Processing
• Mechanism
• Chemical moieties

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 Polymers

• Macromolecule that is formed by linking of repeating units

through covalent bonds in the main backbone
• Properties are determined by
• Molecular weight
• Length
• Backbone structure
• Side chains
• Crystallinity
• Resulting macromolecules have huge molecular weights

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 Polymer terminology

• mer: a unit HOMOPOLYMER

• monomer: one unit
• trimer: three units
• tetramer: four units
• polymer: many units
• pre-polymer: growing towards
being a polymer
• oligomer: few units fixed in size
• homopolymer: polymer made of
one type of monomer

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 Polymer Terminology

• mer: a unit
• monomer: one unit
• trimer: three units
• tetramer: four units
• polymer: many units
• pre-polymer: growing towards being a polymer
• oligomer: few units fixed in size
• homopolymer: polymer made of one type of monomer

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 Difference between Natural Polymers and Synthetic Polymers
Focus of
this course

What is Polymer Science and Engineering?

∙Polymer Synthesis: making a polymer

Materials Polymer Characterization: examining polymer
Science
structure or morphology
Chemistry Polymers Physics Polymer Physics: understanding the polymer chain
conformation, polymer solution thermodynamics,
phase behavior, thermal properties, etc.
Biology Engineering
Polymer Engineering: investigating the mechanical
and rheological properties
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Chemical Structures of Some Common Homopolymers

Homopolymers: polymers
derived from one species of
monomer.

Nomenclature
Conventional: based on source
or structure;
called (poly+”monomer”)

Commercial trade name

7
Chemical Structures of Some Common Homopolymers
Commercial trade name

8
Copolymer
Examples:
Polystyrene-block-poly(methyl methacrylate)
(prepared by living polymerization)

Reacting Y functional group in

homopolymer B with X functional
group in homopolymer A or
prepared by free radical polymerization

Poly(styrene-ran-butadiene)
(prepared by free radical
polymerization)
Poly(styrene-alt-maleic anhydride)
(prepared by free radical
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 Polymer Classification Scheme

• Architecture
• Processing/characteristics
• Polymerization method
• Chemical moieties in polymer

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Polymer Architectures

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 Polymer Configuration

• Stereoisomerism: mers linked together in same order (usually

head-to-tail) but with different spatial arrangements:
• Isotactic configuration: R groups on same side of the molecule

• Syndiotactic configuration: R groups on alternating sides of the molecule

• Atactic configuration: R groups randomly positioned of the molecule

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 Polymers: Processing

• Thermoplastic Polymers: Polymer that soften when heated and

harden when cooled. Process is totally reversible. These
polymers melt as inter-molecular bonding is diminished and the
ease of movement between adjacent chains increases.
• Polyethylene, polyvinylchloride

• Thermosetting Polymers: Polymers that become permanently

hard when cross-linked or networked and do not soften upon
subsequent heating. These polymers do not melt because
chains are held together by primary bonds. Eventually they just
disintegrate or burn.
• Epoxys, polyesters

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 Polymers: Processing

• Elastomers:
• intermediate between thermoplastic and thermosetting
polymers
• some crosslinking
• can undergo extensive elastic deformation
• natural rubber, silicone

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Polymers: Synthesis

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 Polymers: Polymerization Mechanism

• Addition
• monomers react through stages of initiation, propagation,
and termination
• initiators such as free radicals, cations, anions opens the
double bond of the monomer
• monomer becomes active and bonds with other such
monomers
• rapid chain reaction propagates
• reaction is terminated by another free radical or another
polymer

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 Polymers: Polymerization Mechanism

• Addition

initiation

growth

termination

• Termination may occur by:

• two radicalized polymers reacting
• another radicalized monomer
• one initiator (alkoxy radical, •OR, in this case) 17
 Polymers: Polymerization Mechanism

• Examples of some important addition polymers derived from

ethylene
Abbreviation
PE
PP

PVC

PAN

PVAC

Vinyl monomer
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 Polymers: Polymerization Mechanism

PS

PMMA

PVDC

Vinyl monomer

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 Polymers: Polymerization Mechanism

• Condensation Polymers: obtained by the random reaction of two

molecules, each having complementary functional end units
(A)

(B)

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 Condensation vs. Addition

• Addition:
• Difficult to control molecular weight
• Undesirable branching products

• Condensation:
• Molecular weight closely controlled
• Polydispersity ratios close to unity can be obtained

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 Example 2.1

• Lactic acid can be dehydrated to form acrylic acid according to the

following reaction:

• Both of these acids can be used as monomers for polymerization.

Draw the repeating units for each.

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 Example 2.2

• Draw the repeating units when 3mol of hexamethylenediamine (I)

are condensed with 2 mol of adipic acid (II) and 1 mol of sebacic
acid (III)

I II III

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 Polymers: Polymerization Mechanism

PSF

PET (For packaging

applications,
Nylon
particularly plastic
6, 10
bottles)

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 Polymers: Chemical Moieties
• Homochain polymers: polymers made in chain reactions contain only
carbon atoms in the main chain

• Heterochain polymers: polymers made in step reactions may have other

atoms, originating in the monomer functional groups, as part of the chain

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 Example 2.3
• Show how a linear, unsaturated polyester is produced from ethylene glycol
and maleic anhydride and how the linear, unsaturated polyester is
crosslinked with a vinyl monomer such as styrene.

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Recyclable Thermoplastics

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 Summary

• Polymer classification
• Architecture
• Linear
• Cross-linked
• Branched
• Dendritic
• Processing
• Thermoset, thermoplastic, elastomer
• Mechanism
• Addition
• Condensation
• Chemical moieties

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