Polymeric Materials

Overview
Lecture 1

Professor K. Albert Narh

NJIT
Department of Mechanical Engineering

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Agenda

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Overview of Plastics: Video

Definitions (Vocabulary)
Structure of the Molecule: Polymer
Polymerization
Classifications

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Vocabulary
Polymer
Chain Structure
monomer (repeat unit)
Homopolymer
Oligomers (low mw polymer)
Copolymer
Bond energies
Branching
Reactions
Stereoregularity
Addition Polymerization
Isomerism
Condensation
Molar Mass (Molecular Weight)
Polymerization
Number, Weight Ave
Structure
Degree of polymerization
Thermoplastics
(DP)
Thermosets
Polydispersity
Elastomers
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Structure of the Molecule: Polymer

Polymer (from two Greek words: poly- = many,
and -mer from meros = part or member) is a
long molecule consisting of many units (monomers)
joined end to end.
Formed from chemical combinations of: C, H, Cl, F,
N, O, S, Si - in a process known as Polymerization
(joining many mers together)
Monomers are based mainly on ETHYLENE OR
VINYL structure illustrated below
1 [CH2

CH2]n 2

or

2
n

Chemical formula

Structural formula
The vinyl structure presents a linear chain and is often referred to
as aliphatic (hydrocarbon) chain.
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Polymer
A Polymer can also be
characterized as a giant
molecule or macromolecule
because of their large size.
formed by combining large
numbers of low molar mass
molecules
molar mass exceeds 10
kg/mol for reasonable
properties
NOTE: although very large
these molecules cannot be
easily seen.
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Classification of Polymers
Origin: Natural and Synthetic
Method of Polymerization: Addition,
Condensation, Ring-opening
Physical Conformation: linear, branched,
ladder, graft, etc
Configuration (Stereoisomerism or Tacticity):
syndiotactic, isotactic, atactic.
Processing Method
Chemical Family limited value (see page 31
of Belofsky)
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Classification based on origin

Two main types of polymer
Synthetic (produced by polymerization)
Natural, e.g. proteins, cellulose, silk.
NOTE: Some natural polymers can be
produced synthetically. e.g. natural rubber
(i.e. Havea), synthesized as polyisoprene.

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Classification by Method of Polymerization:

(Synthetic Processes)

Two main methods of synthesis:

Addition Polymerization (Chain Growth)
Condensation Polymerization

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Polymerizations: Addition Polymerization

H

R
C

C C

n
H

Polymerization begins by the

action of a chemical initiator.
Monomers are added to each
other by breaking the doublebonds that exist between carbon
atoms. No other chemical byproduct is produced.
e.g. Polyethylene (PE)

Polyethylene
Y+I

1
R
Y

H
C C*

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Y
H

C C

C*

H H

H
n

R H

C C

C*

H H

H
n

H
C C*

H
C

R H

*
R

H
R

Radical reaction:

n-3

Ethylene monomer

Y
H

H
R H

C C

C*

H H

R H

H R

C C

C C

H H

R H

H R

C C

C + H

C C

H H

H
n

H H

H H
n

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Y
n

Addition Polymerizations
(Also known as Chain Growth)

Three types:
Linear addition, e.g. synthesis of PE.
Molecular Re-arrangement, polyurethane
Ring opening or Scissoring, PEO.

The Process involves three steps

Initiation (and reaction)
Propagation
Termination
combination

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Hydrocarbon Series
From gas to solid, an example of linear addition polymerization

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Addition Polymers
polyethylene (PE,
HDPE, LDPE,
LLPE)
polystyrene
polypropylene
polyacrylamide
polyacrylate,
polyacrylic acid,
polymethyl
methacrylate
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polybutadiene
polyisoprene
polybutene
polyvinylchloride
polytetrafluoroethylene
(Teflon)
polyethylene-copropylene-cobutadiene (EPDM)

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Polymerizations: Condensation Polymerization

Two components with end functional groups that react with each
other are mixed.
Loss of low molar mass molecule(s)
e.g. Polyethyethylene Terephthalate (PET)
O
C

OC H3

H3C O

H H

Ethylene glycol

Terephthalic acid

Catalyst

O
C

O
+

C H2
O
C H2

C H3OH

Polyethylene Terephthalate
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Characteristics of Condensation Polymerization

(Also known as Stepwise Polymerization)

Growth throughout matrix involves:

Reaction between functional groups on
monomers.
No initiation and termination steps.
Termination occurs when functional groups
are exhausted.
May contain two or more different groups
along the backbone.

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Condensation Polymerization
Or Step Growth Process
Involves a series of chemical reaction between at least two
different groups. Very often, but not always, it is accompanied
by elimination of a small molecule such as water, ammonia, or
carbon dioxide, which must be removed continuously

Monomers combine to form blocks two units long

Example of series of chemical reaction:
Monomer + Monomer
Dimer
Monomer + Dimer
Trimer
Monomer + Trimer
Tetramer
Dimer + Trimer
Pentamer
n-Mer + m-Mer
(n + m) Mer
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Condensation Polymers
Nylons (Polyamides)
(Reaction of hexamethylene diamine with adipic acid)
H

A structure formula
Nylon 6,6 is shown

H
(CH2)6

C
O

(CH2)4

C
O

OH
n

There are six types of nylons used in engineering

applications:
nylon 6,6 (There are 6 carbon atoms in each residue)
nylon 6,10
nylon 6,12
nylon 6
nylon 11
nylon 12
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Condensation Polymers
Poly(bis phenol A carbonate) (Polycarbonate)

A-A Monomer: Bis phenol A

B-B Monomer: phosgene
A Monomer: End group
O

CH 3
HO

OH

+
Cl

Cl

CH 3

O
CH 3
O

C
O

CH 3

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Condensation Polymers
Kevlar (Aramid)
A-A Monomer: terephthalic acid
HOOC
B-B Monomer:p-phenylene diamine
A Monomer: End group
Nomex
A-A Monomer: isophthalic acid
HOOC
O
H
N

COOH

O
C

N
H

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COOH

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Condensation Polymers
Lexan - poly(bisphenol A carbonate)
Mylar, Dacron - poly(ethylene
terephthalate)
Nylons - polyamides
Kevlar, Nomex - poly(arylamide)
Kapton - (polyimide)

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Characteristics
Addition polymerization
chain reaction
one group added per
reaction
monomer decreases
steadily
DP peaks instantly
high polymer at once
long reaction time gives
high conversion
only polymer and
monomer present
no reaction by-products

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Condensation
polymerization
stepwise reaction
any two molecular
species can react
monomer consumed
early
DP rises steadily
long reaction time gives
high molar mass
all molecular species
(monomers, dimers,
trimers, etc.) present
reaction by-products

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Classification by Physical Conformation:

Polymer Chain Structure
Conformation describes the preferential spatial positions of the
atoms in a molecule. Described by polarity flexibility and
regularity of the molecule.

linear chain

block copolymer

homopolymer
random copolymer

branched chain
homopolymer
copolymer

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AAAAABBBBB

star polymer
comb
graft chain
copolymer

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Polymer Chain Composition

Homopolymer versus Copolymer

Homopolymer
Contains identical
repeat units
(monomers)
condensation
AA + BB
AB

addition
A

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Copolymer
Contains two or more
different repeat units
(monomers)
random
alternating
block
graft

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Homopolymers Based on Addition Polymerization of

Vinyl (CH2) groups

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Copolymers Based on Addition Polymerization

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Molecular Symmetry and the

Tendency to Form Crystals
Gives information about the distribution and spatial arrangement of
the side groups. This is established at the instant of polymerization.

Molecular regularity: molecular characteristic which

distinguishes the crystalline polymers from the non
crystalline.
One form of irregularity is random side branching as in
polyethylene.
Another form of irregularity is asymmetric placement of
the pendant molecule in vinyl polymers - described in
terms of stereo-regularity.
Three forms of stereo-regularity (termed configuration
states) are (a) isotactic, (b) syndiotactic, and (c) atactic.
Three configurational states are illustrated in the next
three slides.
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Configurational States
Stereo-regularity in a vinyl polymer
Configuration permanent
stereostructure.
Rearrangement
requires bond
disruption.

Tacticity

Isotactic
Regular conformation

Syndiotactic
Atactic

Crystals are
always
formed
e.g. isotactic PP

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Configurational States
Stereo-regularity in a vinyl polymer
Configuration permanent
stereostructure.
Rearrangement
requires bond
disruption.

Tacticity
Isotactic

Syndiotactic
Semi-regular
conformation

Atactic

Crystals are
sometimes
formed
e.g. syndiotactic PP,
PS

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Configurational States
Stereo-regularity in a vinyl polymer
Configuration permanent
stereostructure.
Rearrangement
requires bond
disruption.

Tacticity
Isotactic
Syndiotactic

Atactic
Irregular conformation

Crystals are
never formed
e,g, PVC, PS

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Intermolecular Bonding Energies

(Secondary Valence Bonds)
In non-crosslinked polymers (TPs, TPEs), cohesion among
macromolecules is by physical bonding (secondary valence
bonding), not chemical bonding. Intermolecular interactions are a
major factor in the differences in properties.

Examples of Binding Forces

Van der Waals forces (sole intermolecular forces in PTFE and PE)
Dipole interactions (permanent and induced; found in PVC, PMMA,
POM (Acetal))
Hydrogen bonds (e.g. H atom covalently bonded to N atom acts as a
bridge between the N atom and the O atom in PAs) and
Ionic forces (based on electrostatic interactions among differently
charged ions): occurs only in specialty polymers known as ionomers.
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Bond Type

Energy (kJ/mol-1) Bond Length (nm)

Covalent

3 00 - 5 00

0.15 (C-C)
0.11 (C-H)
0.135 (C+O)

van der Waals

10

0 .4

Dipole-Dipole

>10

0 .4

Hydrogen Bond 10-50

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0 .3

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Classification of Polymers by
Chemical Family

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Thermoplastics
Thermosets
Rubber
Elastomers
Natural Macromolecules

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Thermoplastic, Thermoset,
Rubber and Elastomer
Thermoplastics soften when heated and hardened when
cooled. This can be repeated many times.
Thermosets cure and harden when exposed to heat. Since this
change is irreversible, they cannot be re-softened and reshaped.
Natural rubber is one material in a group called elastomers

Elastomers are natural or synthetic polymeric materials that

can be stretched to at least 200% of their original length, at
room temperature, and return quickly to their original length.
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Thermoplastic vs. Thermoset

Thermoplastic
can be formed with
heat/pressure/time
recyclable
crystalline or noncrystalline

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Thermoset
can be formed with
heat/pressure/time
once
not recyclable!

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Rubber and Elastomers

Rubber

Elastomers

butadiene,
isoprene
cross linked
structure
high strength
high recovery

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Thermoplastic
Thermoset
lightly cross
linked
high elongation
(>400%)

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Network in Polymers
Networks
Irreversible: Cross-linked
Reversible: Entanglements
Cross-linked Polymers:

Monomer A of functionality 2
reacts with monomer B of functionality 4 or higher. Four linear
chains of A will meet at each B cross-link.

Thermosets
Vulcanized rubbers: cross linking of
entanglements by sulfur.

Cross-links: covalent bond formed at selected sites

between macromolecules other than along the backbone
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Classification of Thermoplastics Based on

Family Characteristics
Thermoplastics can be further classified into 8 broad
categories listed below - based on family
characteristics:

Polyolefins
Vinyl & Related
Polyamides
Acrylics
Cellulosics
Styrenics (Aromatic hydrocarbon)
Fluoropolymers
Plastics with Special Chain Structures.

The characteristics and typical use/application of each class is briefly

described in a separate handout
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Blends and Polyalloys

Mechanical Mixing of polymer X and polymer Y
No chemical bonding
May be miscible, immiscible or partially miscible
(by compatibilization)
May lead to property synergism

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Synergism of Polyalloys

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Examples of Polymer Blends

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Summary
Addition, condensation, chain growth,
and ionic
Condensation kinetics slow
Condensation polydispersity is high
Composition control is critical
Thermoplastics, thermosets and
elastomers
Polymer Blends and Alloys by
mechanical mixing of polymers.
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