Chapter 5 - Polymers

Pivotal Questions:
- What are polymers?
- How are polymer chains formed?
- What influences the properties of
polymers?
- How are polymers made into consumer
products?
- What happens to discarded polymers?
Definition of Polymers
A polymer is a bonded chain of repeated units with
covalent bonds from end to end.

Poly= many
Mer = unit
Monomers and Oligomers
Monomer – A single building block in a polymer chain
Oligomer – a few monomers bonded together
An oligomer becomes a polymer when the addition of
one more monomer has no measurable effect on
physical properties
Structural Units (or repeat units)
The smallest part of a
polymer chain that
repeats.

The repeat unit of

polystyrene is shown to
the right.

n represent the number

of times the unit is
repeated.
Degree of Polymerization
The number of times
the structural unit is
repeated in the chain.

The degree of
polymerization is
four for the polymer
at the right
Backbones and Substituents
The backbone is the Common Substituents
long repeating center of
the polymer chain -H
-C–C–C–C–C– - OH
Substituents are atoms
- Cl
or groups of atoms that
attach to the backbone. - CH3
- Flows like viscous liquids
when heated and does so
through several reheatings

- Weak Van der Waals

interactions between chains
- Cannot be remelted or
recycled

- Stronger bonding
between adjacent chains

- More resistant to
degradation but harder to
recycle
Random: No Block: Long runs of one
particular order monomer followed by a
run of the other

Alternating: each
monomer is followed by Graft: Chains of one monomer
the other bond as a substituent to chains of
the other
Polymer Blends
Formed by the mechanical mixing of polymers
No bonding between the different monomers
Allow for shaping of properties without new synthesis
process
 Polymer Names
Every polymer has three levels of names:

IUPAC name – based in chemical structure (e.g. – Poly

p-phenylene terephthalamide)

Abbreviated Name (e.g. – PPTA)

Trade names (e.g. – Kevlar (DuPont) or Twaron (Teijin)

Classes of Polymers
There are many classes of polymers, but it is worth
spending time looking at a few of the most important
ones.

Acrylics
Contain at least 85% PAN (polyacrylonitrile)
 Polyamides
Polyamides contain amide groups (CONH2)

There are two primary subclasses

 Aramids - Polyamide in which more than 85% of the amide
groups are bonded to two aromatic rings.

 Nylons - Type of polyamide in which less than 85% of the

amide groups are bonded to aromatic rings
 Polyesters
Polyesters contain at least 85% ester bonds (C-O-C)

Widely used in the clothing and beverage industries

 Polyolefins
Oil-like polymers with only hydrogen and aliphatic
carbon present

Two most significant forms are

Polyethylene (PE)
Polypropylene (PP)
 LDPE vs HDPE
Low-Density High-Density
Polyethylene (LDPE) Polyethylene (HDPE)
Many branches and side Fewer branches
chains Stronger
Easy to melt and More Crystalline
reprocess Milk Bottles, Trash bags
Less strong
Produce bags, toys,
plastic wraps
 HVTPs
High-Volume Thermoplastics are non-polyolefins that
are produced in large quantities.

Two Primary forms:

 Polystyrene (PS)
 Polyvinyl Chloride (PVC)
 Elastomers
Elastomers are polymers that can stretch to at least
200% and return to their original form when the
applied stress has been released.

Major types:
 Polyurethanes
 Aliphatic Thermosets (rubbers)
Glass Transition Temperature (Tg)
Corresponds to the onset of large-scale segmental
motion

Below Tg, the polymer is stiff and glassy

Above Tg, Polymer become rubbery

Polymer Movement Near the

Glass Transition Temperature
 Polymer Formation
Two Primary Reaction Mechanisms

Addition (also called Free-Radical or Chain Growth)

Polymerization

Condensation (also called Step Growth) Polymerization

 Addition Polymerization
Begins with a vinyl
monomer (shown at
right)

Three Stage Process:

Initiation
Propagation Vinyl Monomer
Termination

Addition Polymerize
 Comments on Addition
Each chain made have thousands of repeat units but
will have exactly two end groups

Addition may occur head-to-head or head-to-tail with

the stability of the free-radical controlling the
probability

Termination is also probabilistic and will result in

chains of different lengths
 Condensation Polymerization
Functional groups at the end of the growing polymer
react with those on the monomer, adding one element
to the end of the growing polymer

A small molecule (usually water) is formed as a

byproduct
 O O
HO C C OH HO-CH2CH2-OH

TEREPHTHALIC ACID ETHYLENE GLYCOL

YIELDS

O O
HO C C O-CH2CH2-OH + H2O

POLYETHYLENE TEREPHTHALATE WATER

(PET)

Condensation
Molecular Weight Distributions
Because a polymer has many chains with different
lengths, molecular weight represents an average value
for the sample

Different averages are possible and provide different

kinds of information
 Relative Molecular Mass (RMM)
RMM is defined as

m
RMM
1.0001
The RMM of a chain is the RMM of the repeat unit
times the degree of polymerization
 For a 10,000 unit chain of
polyethylene
RMM = 10,000*[(2*12) + (4*1)] = 280,000

Each PE unit has two carbons (m=12) and 4 hydrogens

(m=1).

Note that this calculation applies only to the

individual chain. Longer or shorter chains would have
a different RMM.
From the histogram, several items
can be determined
The Weight of each fraction is given by
Wi = niMi ,
where ni represents the number of molecules in the ith
fraction.

The total weight (W) of the polymer chains is defined as

W = Wi
 Number Average MW (Mn)
Divides mass by total number of moles

All molecules contribute equally regardless of size

 Number Average MW (Mw)
Normalizes based on weight

Larger molecules dominate behavior

 Example
Example 5-1: Consider a blend made by adding 1 gram
of C5H12 to 1 gram of a large paraffin wax, C100H202.
Determine the number average and weight average
molecular weights for the blend.

Solution: The RMM for C5H12 is (5*12) + (12*1) = 72

g/mol. Since 1 gram of C5H12 is provided, we can
determine the number of moles of C5H12 by dividing by
the RMM.
1 g C5H12/72 g/mol = 1.39 x 10-2 mol of C5H12.
Example Continued
 Factors that Influence Polymer
Properties
Constitution – All of the bonding issues
Primary – Covalent bonds
Secondary – VDW, hydrogen, dipoles

Configuration – Spatial arrangement of atoms that can

only be changed by breaking bonds

Conformation – Spatial arrangement that can be

changed by vibration and rotation
 Bond Type Bond Classification Bond Length Bond Energy
(nm) (kJ/mol) </TBCH>

C-C Covalent—Primary 0.154 347

C-H Covalent—Primary 0.110 414
C-N Covalent—Primary 0.147 305
C-O Covalent—Primary 0.146 360
C-Cl Covalent—Primary 0.177 339
Hydrogen Secondary 0.24–0.32 12.5–29
Bonding

VDW and Secondary 0.3–0.5 8.4 for VDW only to 42

Dipoles for highly polar
 Role of Secondary Bonding
Individual secondary bonds are relatively weak

Highly distance and position dependant

Tens of thousands of secondary bonds act in unison

As a result, secondary bonding usually dominates the

mechanical properties of polymers
 Branching
Branches are
chemically identical to
the main chain but
occur as substituents
Branches make chains
less spatially regular
Easier to melt or
dissolve in solvents
 Configuration
Configurational
isomers occur when
chemically identical
forms cannot be
rotated.
Distinguished as either
R- or S- isomers
S-configuration R-configuration
 Rules for Configuration
1. Place the side group with the highest total atomic
number sticking out. If two groups have the same
atomic number, the physically larger group gets
priority.
2. Rank the remaining groups in order from highest
atomic number to lowest.
3. If moving from the highest atomic number to the
lowest requires a clockwise move, the carbon is labeled
(R). If the move is counterclockwise, the carbon is
labeled (S).
 Asymmetric Carbons
An asymmetric carbon
(one with 4 different
subsituents) must be
present for a
configurational isomer to
exist
None of the molecules to
the right have
asymmetric carbons.
 Isomers in polymer chains
Isomers exist if

But not if
 Tacticity
The relative configuration of adjacent pairs of carbon
atoms (dyads) in the polymer backbone

A syndiotactic dyad has the large

substituents in opposite positions

An isotactic dyad has the large

substituents in the same position

Both syndiotactic and isotactic dyads are spatially regular,

but blends of the two (atactic) are not
 Polymer Crystallinity
Tacticity directly correlates to crystallinity

Polymers do not form Bravais Lattices

At best, polymers may be semi-crystalline with small

regions of order

The crystals act like defects in an amorphous

continuum.
Estimates of Crystallinity Vary with
Technique
X-ray diffraction requires at least 10 layer planes to get
coherent diffraction. Smaller regions of order would
be considered non-crystalline.

Density techniques count any order, even segments of

two chains that happen to be close together.

You must compare like techniques to compare

polymer crystallinities.
 Conformation is a Function of
Energetics
ETot = EB + Eee + Enn + Ekin + Ene

where ETot is the total energy, EB is bond energy

(attractive), Eee is the energy from the interaction of
electron clouds (repulsive), Enn is the energy from the
interaction between nuclei (repulsive), Ekin is a
repulsive kinetic energy term associated with bonding,
and Ene is the energy from the interaction between the
nucleus and electron cloud (attractive).
When the constituents are close (in the eclipsed state), the
energetics are less favorable than when they are far apart
(Trans). This is more important with larger substituents
 Cis State for Butane

0 (360) Least favorable energy

(cis, state (highest energy),
eclipse) large methyl substituent
groups are directly
aligned.
 Gauche State
60 Some interaction between
(trans, the electron clouds from
gauche) the methyl groups, but
there is also more stability
than eclipse.
 Staggered State
120 Electron cloud from the
(cis, –CH3 group begins to
staggered) interact with the electron
cloud of the substit.
hydrogen atoms.
 Trans State

180 Optimal energy state,

(trans, anti) methyl groups are as far
apart as possible.
 Additives
Blended with polymers to enhance or alter a specific
property
Plasticizers – Small molecules that make the polymer
softer and more pliable
Fillers – Inexpensive materials used to reduce cost
Coloring agents – include dyes (that are absorbed into
the polymer) and pigments (that are not)
Stabilizers – Reduce the tendency of the polymer to
rupture when exposed to heat or light via inhibiting free
radical formation
 Processing of Thermoplastics
Extrusion

Wire Coating

Blown Films

Injection Molding

Melt Spinning
Schematic of an Extruder
Coating of a Wire
Injection Molding
Symbol Material Common Uses

<TB>Polyethylene terephthalate Soda bottles

(PET) Carpet fibers

High-density polyethylene Milk bottles

(HDPE) Shampoo bottles
Plastic bags
Hard plastic cups
Sports bottles

Polyvinyl chloride (PVC) Oil bottles

Piping
Castings

Low-density polyethylene Plastic grocery bags

(LDPE) Shrink wrap
Plastic lumber

Polypropylene (PP) Drinking straws

Bottle tops
Plastic furniture

Polystyrene (PS) Packaging

Beverage cups
Meat packaging</TB>
 Recycling Challenges
Need to sort by hand
Collection and gathering issues
Presence of coloring agents, plasticizers, and other
additives
Difficulties with blends and copolymers