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
polymerization) 9
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
18
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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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