Introduction

to Polymers
Chapter 1

Polymers: Introduction
Polymer: High molecular weight molecule made up of a
small repeat unit (monomer).
A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A
Monomer: Low molecular weight compound that can be
connected together to give a poymer
Oligomer: Short polymer chain
Copolymer: polymer made up of 2 or more monomers
Random copolymer: A-B-B-A-A-B-A-B-A-B-B-B-A-A-B
Alternating copolymer: A-B-A-B-A-B-A-B-A-B-A-B-A-B
Block copolymer: A-A-A-A-A-A-A-A-B-B-B-B-B-B-B-B

Polymer
Poly
many

mer
repeat unit (building blocks)

repeat
unit

repeat
unit

H H H H H H
C C C C C C
H H H H H H

H H H H H H
C C C C C C
H Cl H Cl H Cl

Polyethylene (PE)

Poly(vinyl chloride) (PVC)

repeat
unit

H
C
H

H H
C C
CH3 H

H H
C C
CH3 H

H
C
CH3

Polypropylene (PP)

Carbon chain backbone

POLYMER STRUCTURES
What are the general structural and chemical
characteristics of polymer molecules?
What are some of the common polymeric
materials, and how do they differ chemically?
How is the crystalline state in polymers
different from that in metals and ceramics ?

Chemistry and Structure of Polyethylene

Tetrahedral
arrangement
of C-H

Polyethylene is a long-chain hydrocarbon.

Top figure shows repeat unit and chain structures.
Other figure shows zigzag backbone structure.
5

Ancient Polymers
Naturally occurring polymers (those derived
from plants and animals) have been used for
centuries.
Wood
Rubber
Cotton
Wool
Leather
Silk
Oldest known uses
Rubber balls used by Incas

Cellulose

Cellulose is a highly abundant organic compound.

Extensive hydrogen bonding between the chains causes
native celluose to be roughly 70% crystalline. It also
raises the melting point (>280C) to above its
combustion temperature.
Cellulose serves as the principal structural component of
green plants and wood.
Cotton is one of the purest forms of cellulose and has
been cultivated since ancient times.
Cotton also serves (along with treated wood pulp) as the
source the industrial production of cellulose-derived
materials which were the first "plastic" materials of
commercial importance.

Rubber

A variety of plants produce a sap consisting of a colloidal

dispersion of cis-polyisoprene. This milky fluid is especially
abundant in the rubber tree (Hevea); it drips when the bark is
wounded.
After collection, the latex is coagulated to obtain the solid
rubber. Natural rubber is thermoplastic, with a glass transition
temperature of 70C.
Raw natural rubber tends to be sticky when warm and brittle
when cold, so it was little more than a novelty material when first
introduced in Europe around 1770.
It did not become generally useful until the mid-nineteenth
century when Charles Goodyear found that heating it with sulfur
a process he called vulcanization could greatly improve its
properties.
cispolyisoprene

Common Polyolefins
Monomer
Ethylene

Polymer
Polyethylene

CH3

H3C

CH3

CH3

Polypropylene
Propylene

CH3 CH3 CH3 CH3 CH3 CH3 CH3

CH3

Ph
Polystyrene
Styrene

Ph

Ph

Ph

Ph

Vinyl Chloride

Tetrafluoroethylene

Ph

Ph

Ph
CH3

Cl

F2C CF2

Repeat unit

Poly(vinyl chloride)

Cl

F3C
Poly(tetrafluoroethylene): Teflon

Cl
F2
C

C
F2

Cl
F2
C

C
F2

Cl
F2
C

C
F2

Cl
F2
C

C
nF
2

Cl
F2
C

C
F2

Cl
F2
C

C
F2

CF3

Polyesters, Amides, and

Urethanes
Monomer
Polymer
O
HO2C

CO2H

Terephthalic
acid
O

OH

HO
Ethylene
glycol

Poly(ethylene terephthalate

Ester
O

NH2
OH H2N
4
1,6-Diaminohexane

HO

Nylon 6,6

O
CO2H H2N

HO2C

NH2

1,4-Diamino
benzene

Terephthalic
acid

H2
C

OCN

NCO

4,4-diisocyantophenylmethane
O
HO

H
N

H2
C

H2 H2
O C C O H

HO

HO
4
Adipic Acid

HO

O
4

N
H

N
4
H
Amide
O

H
N

Kevlar

H
n

H
N H
n

OH
HO
Spandex
Ethylene
glycol
O
H2 H2
H
N
O C C O H
n

Urethane linkage

Natural Polymers
Polymer

Monomer

Isoprene
H OH
HO
HO

Polyisoprene:
Natural rubber

HO

H OH
H

OH
H
H
-D-glucose

OH

Poly(-D-glycoside):
cellulose

O
O

R
Amino Acid

H3N

OH
Nucleotide
Base = C, G, T, A

O
Rn+1

OH
Rn+2

O
O

O
oligonucleic acid
DNA

H
N

O P O

Base

OH

OH
H

H
N

R1
DNA

O P O
O

Polyamino acid:
protein

H
H

O
H3N

HO

O
HO

DNA

Base

What Makes Polymers Unique?

Really big molecules (macromolecules) like
polymers have very different properties than
small molecules
Chain entanglement: Long
polymer chains get entangled with
each other.

When the polymer is melted, the

chains can flow past each other.
Below the melting point, the chains
can move, but only slowly. Thus the
plastic is flexible, but cannot be easily
stretched.
Below the glass transition point, the
chains become locked and the
polymer is rigid

Linear Polymer

Physical Properties

Stretch

The chains can be stretched, which causes

them to flow past each other. When released,
the polymer will not return to its original form.

Cross-Linked Polymer

Stretch

Relax

The cross-links hold the chains together.

When released, the polymer will return to it's
original form.

Polymer Microstructure

Polyolefinswithsidechainshavestereocentersoneveryothercarbon
CH3
n

CH3 CH3 CH3 CH3 CH3 CH3 CH3

Withsomanystereocenters,thestereochemistrycanbecomplex.There
arethreemainstereochemicalclassificationsforpolymers.
Atactic: random orientation

Isotactic: All stereocenters have same orientation

Syndiotactic: Alternating stereochemistry

How to Determine Microstructure?

CNMRisaverypowerfulwaytodeterminethe
microstructureofapolymer.
13

13C

NMR shift is sensitive to the two

stereocenters on either side on sptectrometers
> 300 MHz. This is called pentad resolution.

mmrm pentad
m = meso (same orientation)
r = racemic (opposite orientation)

CNMRspectrumofCH3
regionofatactic
13

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, gooey material
Isoatactic PP is high melting (176), crystalline,
tough material that is industrially useful
Syndiotactic PP has similar properties, but is
very clear. It is harder to synthesize

Hydrocarbon Molecules
Many organic materials are
hydrocarbons (composed of hydrogen
and carbon).
Most polymers are made up of H and C.
The bonds between the hydrocarbon
molecules are covalent.
Each carbon atom has 4 electrons that
may be covalently bonded, the hydrogen
atom has 1 electron for bonding.
A single covalent bond exists when each
of the 2 bonding atoms contributes one
electron (ex: methane, CH4).

Saturated Hydrocarbons
Each carbon has a
single bond to 4 other
atoms; the 4 valence
electrons are bonded,
the molecule is stable.
Examples are seen in
the table.
The covalent bonds in
each molecule are
strong, but only weak
hydrogen and van der
Waals bonds exist
between the
molecules.

Most of these hydrocarbons have relatively

low melting and boiling points.
However, boiling temperatures rise with
increasing molecular weight.

Unsaturated Hydrocarbons
Double & triple bonds are somewhat unstable
involve sharing 2 or 3 pairs of electrons,
respectively. They can also form new bonds
Double bond found in ethylene - C2H4

H
C C

H C C H

Triple bond found in acetylene - C2H2

Isomerism
Two compounds with same chemical formula can
have different structures (atomic arrangements).
for example: C8H18
normal-octane
H H H H H H H H
H C C C C C C C C H

= H3C CH2 CH2 CH2 CH2 CH2 CH2 CH3

H H H H H H H H

H3C ( CH2 ) CH3

2,4-dimethylhexane

CH3
H3C CH CH2 CH CH3
CH2
CH3

Monomer
Synthesis/polymerization
Long chain polymer
Thenature
ofthe
catalyst
used

Gas, liquid,
solid
Thewaythe
chaingrow
thefinal
product

Theimportantofpolymerization
Affectthestructure
henceproperties
Sometimescanconvert
monomersdirectlytofinish
product

ThreeStageProcessforChainGrowthPolymerization

Step-Growth Polymerization
n

Stage 1

Consumption
of monomer

Stage 2
Combination
of small fragments

Stage 3
Reaction of
oligomers to give
high molecular
weight polymer

Addition (Chain) Polymerization

Initiation
Propagation

Termination

43

Condensation (Step) Polymerization

44

Polymerization
Free radical polymerization: ethylene gas reacts with
the initiator (catalyst). (R. is the unpaired electron)
R

H H
H H

H H

C C

R C C

H H
monomer
(ethylene)

free radical

R C C

H H

initiation

H H
Monomer refers to the small molecule from which a
polymer is synthesized.

H H

H H H H

C C

R C C C C

H H

H H H H
dimer

propagation

Some Common Addition Polymers

Some Condensation Polymers

MOLECULAR WEIGHT
Molecular weight, M: Mass of a mole of chains.
Low M
high M

Polymers can have various lengths depending on the number

of repeat units.
During the polymerization process not all chains in a polymer
grow to the same length, so there is a distribution of
molecular weights. There are several ways of defining an
average molecular weight.
The molecular weight distribution in a polymer describes the
relationship between the number of moles of each polymer
species and the molar mass of that species.

Molecular Weight of Polymers

Unlikesmallmolecules,polymersaretypicallyamixtureof
differentlysizedmolecules.Onlyanaveragemolecularweight
canbedefined.

Viscosity average M.W. (Mv):

Average determined by viscosity

Mv Mn
Mw

#
o
f
m
o
le
cu
le
s

Measuring molecular weight

Size exclusion chromatography
Viscosity
Measurements of average molecular
weight (M.W.)
Number average M.W. (Mn): Total
weight of all chains divided by # of
chains
Weight average M.W. (Mw):
Weighted average. Always larger
than Mn

increasing molecular weight

What the Weights Mean

Mn:Thisgivesyouthetrueaverageweight

Let's say you had the following polymer sample:

2 chains: 1,000,000 Dalton 2,000,000
5 chains: 700,000 Dalton
3,500,000
10 chains: 400,000 Dalton 4,000,000
4 chains: 100,000 Dalton
400,000
2 chains: 50,000 Dalton
100,000
10,000,000
10,000,000/23 = 435,000 Dalton
1 Dalton = 1 g/mole

Weight Average Molecular Weight

Mw:Sincemostofthepolymermassisintheheavier
fractions,thisgivestheaveragemolecularweightofthemost
abundantpolymerfractionbymass.
2,000,000
0.20 1,000,000 200,000
10,000,000
3,500,000
0.35 700,000 245,000
10,000,000
4,000,000
0.40 400,000 160,000
10,000,000
400,000
0.04 100,000 4,000
10,000,000
100,000
0.01 50,000 500
10,000,000
Total 609,500

Degree of Polymerization, DP
DP = average number of repeat units per chain

Mn
DP
m
where m repeat unit molecular weight

Ex. problem 4.1b,

for PVC: m = 2(carbon) + 3(hydrogen) + 1(Clorine)

(from front of book)
= 2(12.011) + 3(1.008) + 1(35.45)
= 62.496 g/mol
DP = 21,150 / 62.496 = 338.42

Polymer Chain Lengths

Many polymer properties are affected by the
length of the polymer chains. For example, the
melting temperature increases with increasing
molecular weight.
At room temp, polymers with very short chains
(roughly 100 g/mol) will exist as liquids.
Those with weights of 1000 g/mol are typically
waxy solids and soft resins.
Solid polymers range between 10,000 and several
million g/mol.
The molecular weight affects the polymers
properties (examples: elastic modulus & strength).

Polymers Molecular Shape

Straight (b) and twisted (c) chain segments are

generated when the backbone carbon atoms (dark
circles) are oriented as in the figure above.
Chain bending and twisting are possible by rotation of
carbon atoms around their chain bonds.
Some of the polymer mechanical and thermal
characteristics are a function of the chain segment
rotation in response to applied stresses or thermal
vibrations.

Molecular Structures for Polymers

secondary

bonding

Linear

Branched

Cross-Linked

Network

The physical characteristics of a polymer depend

also on differences in the structure of the
molecular chains (other variables are shape and
weight).
Linear polymers have repeat units joined end to
end in single chains. There may be extensive van
der Waals and hydrogen bonding between the
chains. Examples: polyethylene, PVC, nylon.

Molecular Structures- Branched

Linear

Branched

Cross-Linked

Network

Where side-branch chains have connected to main chains,

these are termed branched polymers. Linear structures
may have side-branching.
HDPE high density polyethylene is primarily a linear
polymer with minor branching, while LDPE low density
polyethylene contains numerous short chain branches.
Greater chain linearity and chain length tend to increase
the melting point and improve the physical and mechanical
properties of the polymer due to greater crystallinity.

Molecular Structures
Cross-linked, Network
secondary

bonding

Linear

Branched

Cross-Linked

Network

In cross-linked polymers, adjacent linear chains

are joined to one another at various positions by
covalent bonding of atoms. Examples are the
rubber elastic materials.
Small molecules that form 3 or more active
covalent bonds create structures called network
polymers. Examples are the epoxies and
polyurethanes.

Thermoplastics and Thermosets

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
and rising temperature. Thermoplastics and Thermosets 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).

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.

Examples of Thermoplastics

More Examples of Thermoplastics

Polymer

http://www2.dupont.com/Teflon/en_US/index.html
http://en.wikipedia.org/wiki/Teflon

Specific Thermoplastic Properties

Thermoset data

Thermoset Properties

Specific Elastomeric Properties

Elastomers, often referred to as rubber, can be a thermoplastic or a thermoset
depending on the structure. They are excellent for parts requiring flexiblity,
strength and durability: such as automotive and industrial seals, gaskets and
molded goods, roofing and belting, aircraft and chemical processing seals,
food, pharmaceutical and semiconductor seals, and wire and cable coatings.

Thermoplastic vs Thermoset
Thermoplastics:
--little cross linking
--ductile
--soften with heating
--polyethylene
polypropylene
polycarbonate
polystyrene

T
mobile
liquid

Thermosets:
--large cross linking
(10 to 50% of mers)
--hard and brittle
--do NOT soften with heating
--vulcanized rubber, epoxies,
polyester resin, phenolic resin

viscous
liquid

crystalline
solid

Callister,
rubber
Fig. 16.9
tough
plastic

partially
crystalline
solid

Molecular weight

Tm
Tg

Crystallinity in Polymers
The crystalline state may
exist in polymeric materials.
However, since it involves
molecules instead of just
atoms or ions, as with metals
or ceramics, the atomic
arrangement will be more
complex for polymers.
There are ordered atomic
arrangements involving
molecular chains.
Example shown is a
polyethylene unit cell
(orthorhombic).

Crystal Structures

Fe3C iron carbide

orthorhombic crystal
structure

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

The effect of temperature on the structure and

behavior of thermoplastics.

Polymer Crystallinity
Polymers are rarely 100% crystalline
Difficult for all regions of all chains to
become aligned
crystalline
region

Degree of crystallinity

expressed as % crystallinity.
-- Some physical properties
depend on % crystallinity.
-- Heat treating causes
crystalline regions to grow
and % crystallinity to
increase.

amorphous
region

Types of Polymers
Polymer Classifications
Thermoset: cross-linked polymer that cannot be
melted (tires, rubber bands)
Thermoplastic: Meltable plastic
Elastomers: Polymers that stretch and then return to
their original form: often thermoset polymers
Thermoplastic elastomers: Elastic polymers that can
be melted (soles of tennis shoes)
Polymer Families
Polyolefins: made from olefin (alkene) monomers
Polyesters, Amides, Urethanes, etc.: monomers linked
by ester, amide, urethane or other functional groups
Natural Polymers: Polysaccharides, DNA, proteins