Polymers: Refresher

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 The Graduate (1967)

Mr. McGuire: I just want to say one word to you. Just one
word.
Benjamin: Yes, sir.
Mr. McGuire: Are you listening?
Benjamin: Yes, I am.
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Mr. McGuire: Plastics.
 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.
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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

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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 (>280°C) 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 –70°C.
 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.

cis-polyisoprene
 Addition (Chain) Polymerization

– Initiation

– Propagation

– Termination

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Condensation (Step) Polymerization

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Polymerization
 Free radical polymerization: ethylene gas reacts
with the initiator (catalyst). (“R.” is the unpaired
electron)
H H H H
R + C C R C C initiation
H H H H
free radical monomer
Monomer refers to the small molecule from which a
(ethylene)
polymer is synthesized.

H H H H H H H H
R C C + C C R C C C C propagation
H H H H H H H H
dimer

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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.
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MOLECULAR WEIGHT
DISTRIBUTION

M n  x i M i
M w  w i M i

__
Mn = the number average molecular weight (mass)
Mi = mean (middle) molecular weight of size range i
xi = number fraction of chains in size range 13i
wi = weight fraction of chains in size range i
Polydispersity index (PDI)
 It is a measure of the breadth of the molecular-weight
distribution and is given by the ratios of molecular-weight
averages.
 PDI = Mw/Mn
 Example

A polydisperse sample of polystyrene is prepared by mixing three

monodisperse samples in the following proportions:

1g 10,000 molecular weight

2g 50,000 molecular weight
2g 100,000 molecular weight

Using this information, calculate the number-

average molecular weight (Mn), weight-average
molecular weight (Mw), and PDI of the mixture.
Answer:
Mn= 31,250 Mw=62,000 PDI = 1.98
 Degree of Polymerization, DP
DP = average number of repeat units per chain

Mn
DP 
m
where m  repeat unit molecular weight

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 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 polymer’s properties (examples:
elastic modulus & strength).

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 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.

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 Chain End-to-End Distance, r
 Representation of a single polymer chain
molecule that has numerous random kinks
and coils produced by chain bond rotations;
it is very similar to a heavily tangled fishing
line.
 “r” is the end to end distance of the
polymer chain which is much smaller than
the total chain length.

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Glass transition Temperature (Tg)
 The glass transition is the reversible transition in
amorphous materials from a hard and relatively brittle
"glassy" state into a molten or rubber-like state, as the
temperature is increased.
 The glass-transition temperature Tg of a material
characterizes the range of temperatures over which this
glass transition occurs. It is always lower than the
melting temperature, Tm.
 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.

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 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. 22
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.

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 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).

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 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.

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Examples of Thermoplastics

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 More Examples of Thermoplastics
Polymer

PTFE

http://www2.dupont.com/Teflon/en_US/index.html
Specific Thermoplastic Properties
Thermoset data
 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
T
• Thermoplastics: Callister,
viscous rubber
--little cross linking Fig. 16.9
mobile liquid Tm
--ductile tough
liquid
--soften with heating plastic
--polyethylene
Tg
polypropylene
partially
polycarbonate crystalline
polystyrene crystalline
solid
solid

Molecular weight
• Thermosets:
--large cross linking
(10 to 50% of mers)
--hard and brittle
--do NOT soften with heating
--vulcanized rubber, epoxies,
polyester resin, phenolic resin 3
 Copolymers
two or more monomers random
polymerized together
 random – A and B randomly
positioned along chain
 alternating – A and B
alternating
alternate in polymer chain
 block – large blocks of A
units alternate with large block
blocks of B units
 graft – chains of B units
grafted onto A backbone

A– B– graft
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 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).
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©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning ™ is a trademark used herein under license.
behavior of thermoplastics.
The effect of temperature on the structure and
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

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 Plastic Recycling Symbols
In 1988 the Society of the Plastics Industry developed a
numeric code to provide a uniform convention for
different types of plastic containers.
These numbers can be found on the underside of
containers.
1. PET; PETE (polyethylene terephthalate): plastic water and soda
bottles.
2. HDPE (high density polyethylene): laundry/dish detergent
3. V (Vinyl) or PVC: Pipes, shower curtains
4. LDPE (low density polyethylene): grocery bags, sandwich bags
5. PP (polypropylene): Tupperware®, syrup bottles, yogurt cups,
6. PS (polystyrene): Coffee cups, disposable cutlery
7. Miscellaneous: any combination of 1-6 plastics

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